Halo-containing anion exchange membranes and methods thereof

ABSTRACT

The present invention relates to functionalized polymers including a poly(phenylene) structure having modifications suitable for an anion exchange membrane. Exemplary modifications include use of a cationic moiety and a halo moiety. Methods and uses of such structures and polymers are also described herein.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of prior application Ser. No.15/398,545, filed Jan. 4, 2017, which in turn claims the benefit of U.S.Provisional Application No. 62/274,569, filed Jan. 4, 2016, each ofwhich is hereby incorporated by reference in its entirety.

STATEMENT OF GOVERNMENT INTEREST

This invention was made with Government support under Contract No.DE-NA0003525 awarded by the United States Department of Energy/NationalNuclear Security Administration. The Government has certain rights inthe invention.

FIELD OF THE INVENTION

The present invention relates to functionalized polymers including apoly(phenylene) structure having modifications suitable for an anionexchange membrane. Exemplary modifications include use of a cationicmoiety and a halo moiety. Methods and uses of such structures andpolymers are also described herein.

BACKGROUND OF THE INVENTION

Polymers including a poly(phenylene) backbone can provide improvedproperties, including enhanced chemical stability and/or strength. Thus,such robust polymers have been examined for use in fuel battery cells.However, further use as an anion exchange membrane will require chemicalfunctionalities that impart binding to anionic carriers (e.g., hydroxideor carbonate anions), while maintaining the durability provided by thebackbone. Additional starting materials, compositions, and methods toaddress such concerns are desired.

SUMMARY OF THE INVENTION

The present invention relates to polymer compounds and compositionshaving a poly(phenylene) structure in combination with a cationic moietyand/or a halo group to impart characteristics beneficial for an anionexchange membrane. For such a membrane, the composition should becapable of binding an anion, e.g., by use of a cationic moiety withinthe composition. In another instance, the composition should besufficiently hydrophobic to reduce affinity with water, e.g., by use ofa halo group within the composition.

Hydrophobicity can be one non-limiting way to control water affinity ofthe composition. In some instances, the polymer composition herein canbe employed as an anion exchange membrane, which in turn can be employedwithin a fuel cell. A fuel cell can exhibit poor performance due toflooding, which can occur when the anionic exchange membrane displayshigh affinity to water. Thus, performance can be improved by employing asufficiently hydrophobic polymer composition, which also displaysbinding to an anion carrier.

Accordingly, in one aspect, the present invention features a composition(e.g., a molecule, a monomer, a polymer, an article, etc.) including theformula (I), having the formula (I), or including a structure having theformula (I):

or a salt thereof (e.g., a cationic salt, such as a sodium salt, or aform thereof including a counter ion, such as a hydroxide).

In some embodiments, each and every R^(AF) includes a cationic moiety ora halo. In other embodiments, at least one R^(AF) is R^(A) (e.g., anaryl, an alkyl, a heteroaryl, or a heteroalkyl substituted with thecationic moiety). In yet other embodiments, at least one R^(AF) is R^(F)(e.g., an aryl, an alkyl, a heteroaryl, or a heteroalkyl substitutedwith the halo). In some embodiments, the cationic moiety includes anonium cation (e.g., any described herein, such as an ammonium cation).

In some embodiments, each R^(AF) includes, independently, optionallysubstituted alkyl (e.g., C₁₋₁₂ alkyl), optionally substituted haloalkyl(e.g., C₁₋₁₂ haloalkyl), optionally substituted perfluoroalkyl (e.g.,C₁₋₁₂ perfluoroalkyl), optionally substituted heteroalkyl (e.g., C₁₋₁₂heteroalkyl), halo, optionally substituted aryl (e.g., C₄₋₁₈ aryl),optionally substituted alkaryl (e.g., C₁₋₁₂ alk-C₄₋₁₈ aryl or C₁₋₆alk-C₄₋₁₈ aryl), optionally substituted arylalkoxy (e.g., C₄₋₁₈aryl-C₁₋₁₂ alkoxy or C₄₋₁₈ aryl-C₁₋₆ alkoxy), optionally substitutedaryloxy (e.g., C₄₋₁₈ aryloxy, optionally including one or more halo orhaloalkyl), optionally substituted aryloxycarbonyl (e.g., C₅₋₁₉aryloxycarbonyl), optionally substituted aryloyl (e.g., C₇₋₁₁ aryloyl orC₅₋₁₉ aryloyl), optionally substituted arylcarbonylalkyl (e.g., C₄₋₁₈arylcarbonyl-C₁₋₁₂ alkyl or C₄₋₁₈ arylcarbonyl-C₁₋₆ alkyl), optionallysubstituted arylsulfonyl (e.g., C₄₋₁₈ arylsulfoyl), or optionallysubstituted arylsulfonylalkyl (e.g., C₄₋₁₈ arylsulfonyl-C₁₋₁₂ alkyl orC₄₋₁₈ arylsulfonyl-C₁₋₆ alkyl).

In some embodiments, each R¹ or R³ is, independently, H, halo,optionally substituted C₁₋₁₂ alkyl, optionally substituted C₁₋₁₂haloalkyl, optionally substituted C₁₋₁₂ perfluoroalkyl, optionallysubstituted C₁₋₁₂ heteroalkyl, R^(S), R^(P), R^(C), or R^(E), whereR^(S) is an acidic moiety including a sulfonyl group, R^(P) is an acidicmoiety including a phosphoryl group, R^(C) is an acidic moiety includinga carbonyl group, and R^(E) is an electron-withdrawing moiety; eachAr^(L) is, independently, a bivalent linker including optionallysubstituted arylene; each Ar^(M) is, independently, a bivalent linkerincluding optionally substituted arylene; each q is, independently, aninteger of from 0 to 5 (e.g., where each q for R¹ is, independently, 0or 1); each a is, independently, an integer of from 0 to 5, wherein atleast one a is not 0; and m is an integer of from about 1 to 1000 (e.g.,from about 1 to 500). In further embodiments, at least one R¹ or Ar^(L)in formula (I) includes R^(S), R^(P), R^(C), or R^(E). In someembodiments, q for R¹ is 1. In some embodiments, a for Ar^(L) is aninteger of from 0 to 5; and/or a for all other aryl groups is an integerof from 1 to 5. In some embodiments, each and every R³ is,independently, R^(H), R^(S), R^(P), R^(C), or R^(E).

In some embodiments, at least one R^(AF) an optionally substituted arylgroup. In other embodiments, each and every R^(AF) comprises anoptionally substituted aryl group. In yet other embodiments, at leastone R^(AF) includes an optionally substituted aryl group including oneor more halo groups. In other embodiments, at least one R^(AF) includesan optionally substituted alkyl group including one or more halo groups.In some embodiments, at least one R^(AF) includes an optionallysubstituted aryl group including one or more cationic moieties. In otherembodiments, at least one R^(AF) includes an optionally substitutedalkyl group including one or more cationic moieties.

In some embodiments, R^(AF) is -L^(A)-Ar^(AF). In other embodiments,R^(AF) is -L^(A)-Ak^(AF). In one instance, Ar^(AF) is an optionallysubstituted aryl including the cationic moiety or the halo (e.g.,substituted with one or more substituents selected from the group ofhalo, cyano, optionally substituted haloalkyl, optionally substitutedperfluoroalkyl, optionally substituted nitroalkyl, and optionallysubstituted alkyl). In another instance, Ak^(AF) is an optionallysubstituted alkyl including the cationic moiety or the halo; or anoptionally substituted heteroalkyl including the cationic moiety or thehalo (e.g., substituted with one or more substituents selected from thegroup of halo, cyano, optionally substituted haloalkyl, optionallysubstituted perfluoroalkyl, optionally substituted nitroalkyl, andoptionally substituted alkyl).

In one instance, L^(A) is a covalent bond, carbonyl (—C(O)—), oxy (—O—),thio (—S—), azo (—N═N—), phosphonoyl (—P(O)H—), phosphoryl (—P(O)<),sulfonyl (—S(O)₂—), sulfonyl (—S(O)—), sulfonamide (e.g., —SO₂—NR^(L3)—or —NR^(L3)—SO₂—, where R^(L3) is H, optionally substituted alkyl,optionally substituted haloalkyl, optionally substituted alkoxy,optionally substituted alkaryl, optionally substituted aryl, or halo),imino (—NH—), imine (e.g., —CR^(L1)═N—, where R^(L1) is H or optionallysubstituted alkyl), phosphine (e.g., —PR^(L3)— group, where R^(L3) is Hor optionally substituted alkyl), nitrilo (e.g., —NR^(L3)—, where R^(L3)is H, optionally substituted alkyl, optionally substituted haloalkyl,optionally substituted alkoxy, optionally substituted alkaryl,optionally substituted aryl, or halo), optionally substituted C₁₋₁₂alkylene, optionally substituted C₁₋₁₂ alkyleneoxy, optionallysubstituted C₁₋₁₂ heteroalkylene, optionally substituted C₁₋₁₂heteroalkyleneoxy, optionally substituted C₄₋₁₈ arylene, or optionallysubstituted C₄₋₁₈ aryleneoxy (e.g., —(CR^(L1)R^(L2))_(La)—,—C(O)NR^(L3)—, —NR^(L3)C(O)—, —SO₂—NR^(L3)—, —NR^(L3)—SO₂—,—(CR^(L1)R^(L2))_(La)—C(O)—NR^(L3)—, —(CR^(L1)R^(L2))_(La—NR)^(L3)—C(O)—, —(CR^(L1)R^(L2))_(La)—SO₂—NR^(L3)—, or—SO₂—NR^(L3)—(CR^(L1)R^(L2))_(La)—, where each of R^(L1), R^(L2), andR^(L3) is, independently, H, optionally substituted alkyl, optionallysubstituted haloalkyl, optionally substituted alkoxy, optionallysubstituted alkaryl, optionally substituted aryl, or halo).

In other embodiments, R^(S) is —SO₂—OH, —SO₂—R^(S1), —R^(SA)—SO₂—R^(S1),—SO₂—R^(Ar), —R^(SA)—SO₂—R^(Ar), —SO₂NR^(N1)R^(N2),—N(R^(N1))—SO₂—R^(S3), —SO₂—R^(S3), —SO₂—NR^(N1)—R^(S2), or—SO₂—NR^(N1)—SO₂—R^(S3) (e.g., where each of R^(S1), R^(S2), R^(S3),R^(Ar), R^(SA), R^(N1), and R^(N2) is any described herein).

In some embodiments, R^(C) is —CO₂H, —C(O)—R^(C1), or—R^(CA)—C(O)—R^(C1) (e.g., where each of R^(C1) and R^(CA) is anydescribed herein).

In some embodiments, R^(P) is —P(O)(OH)₂, —O—PO(OH)₂, —P(O)HR^(P1),—P(O)<R^(P1)R^(P2), —P(O)<R^(Ar)R^(P2), —P(O)<R^(Ar)R^(Ar),—R^(PA)—P(O)<R^(P1)R^(P2), —R^(PA)—P(O)<R^(Ar)R^(P2),—R^(PA)—P(O)<R^(Ar)R^(Ar), —O—P(O)<R^(P1)R^(P2), —O—P(O)<R^(Ar)R^(P2),or —O—P(O)<R^(Ar)R^(Ar) (e.g., where each of R^(P1), R^(P2), R^(Ar), andR^(PA) is any described herein, and where each R^(Ar) can be the same ordifferent).

In some embodiments, R^(E) is optionally substituted C₇₋₁₁ aryloyl,optionally substituted C₆₋₁₈ aryl, carboxyaldehyde, optionallysubstituted C₂₋₇ alkanoyl, optionally substituted C₁₋₁₂ alkyl,optionally substituted C₁₋₁₂ haloalkyl, optionally substituted C₂₋₇alkoxycarbonyl, nitro, nitroso, cyano, sulfo, carboxyl, and quaternaryammonium (e.g., any described herein). In other embodiments, R^(E)includes or is substituted by perfluoroalkyl (e.g., C₁₋₁₂perfluoroalkyl).

In some embodiments, the composition includes a structure having any oneof formulas (Ia) to (IIj), or a salt thereof or a form thereof includinga counter ion. In other embodiments, each R^(AF) is, independently,R^(A) (i.e., a functional group including a cationic moiety) or R^(F)(i.e., a functional group including a halo). In particular embodiments,the functional group for R^(A) and R^(F) is, independently, selectedfrom the group of an optionally substituted alkyl, an optionallysubstituted heteroalkyl, an optionally substituted aryl, an optionallysubstituted heteroaryl, an optionally substituted alkaryl, an optionallysubstituted aryloxy, and an optionally substituted aryloyl.

In some embodiments, the composition includes a structure having any oneof formulas (I-1) to (I-8), (IV-3), (IV-5), (IV-8), (IV-10), or (IV-11),or a salt thereof or a form thereof including a counter ion. In someembodiments, each and every R^(AF1), if present, comprises the cationicmoiety or the halo. In other embodiments, each and every if present,comprises the cationic moiety. In yet other embodiments, each and everyR^(A1), if present, comprises the halo.

In some embodiments, R^(F1) is the halo, an optionally substituted arylhaving the halo, an optionally substituted alkyl having the halo, or anoptionally substituted heteroalkyl having the halo. In otherembodiments, R^(A1) is the cationic moiety, an optionally substitutedaryl having the cationic moiety, an optionally substituted alkyl havingthe cationic moiety, or an optionally substituted heteroalkyl havingwith the cationic moiety.

In another aspect, the present invention features a composition (e.g., amolecule, a monomer, a polymer, an article, etc.) including the formula(VI), having the formula (VI), or including a structure having theformula (VI):

or a salt thereof (e.g., a cationic salt, such as a sodium salt) or aform thereof including a counter ion (e.g., an anion, such as anydescribed herein). In some embodiments, each of R^(AF) (e.g., R^(A) andR^(F)), R^(H), R¹, R³, Ar^(L), Ar^(M), q, a, m, n, L′, and R^(L) is,independently, any described herein. In some embodiments, each R^(L) is,independently, an electrophilic reactive end group (e.g., any herein,such as optionally substituted C₇₋₁₁ aryloyl or optionally substitutedC₆₋₁₈ aryl). In further embodiments, at least one R¹ or Ar^(L) or Ar^(M)in formula (VI) includes R^(AF), R^(A), R^(F), R^(H), R^(S), R^(P),R^(C), or R^(E).

In yet another aspect, the present invention features a composition(e.g., a molecule, a monomer, a polymer, an article, etc.) including theformula (VII), having the formula (VII), or including a structure havingthe formula (VII):

or a salt thereof (e.g., a cationic salt, such as a sodium salt) or aform thereof including a counter ion (e.g., an anion, such as anydescribed herein). In some embodiments, each of R^(AF) (e.g., R^(A) orR^(F)), R¹, R³, Ar^(M), q, a, m, n, L, and Ar* is, independently, anydescribed herein. In some embodiments, each of m and n is,independently, an integer of from about 1 to 1000 (e.g., from about 1 to500); L is a linking segment; and Ar* is a hydrophobic segment. Infurther embodiments, at least one R¹ or Ar^(L) or Ar^(M) in formula(VII) includes R^(AF), R^(A), R^(F), R^(H), R^(S), R^(P), R^(C), orR^(E).

In yet another aspect, the present invention features a composition(e.g., a molecule, a monomer, a polymer, an article, etc.) including theformula (VIII), having the formula (VIII), or including a structurehaving the formula (VIII):

or a salt thereof (e.g., a cationic salt, such as a sodium salt) or aform thereof including a counter ion (e.g., an anion, such as anydescribed herein). In some embodiments, each of R^(AF) (e.g., R^(A) orR^(F)), R¹, R³, R^(L), Ar^(L), Ar^(M), q, a, m, n, L, and Ar* is,independently, any described herein. In some embodiments, each of m andn is, independently, an integer of from about 1 to 1000 (e.g., fromabout 1 to 500); L is a linking segment; and Ar* is a hydrophobicsegment. In further embodiments, at least one R¹ or Ar^(L) or Ar^(M) informula (VIII) includes R^(AF), R^(A), R^(F), R^(H), R^(S), R^(P),R^(C), or R^(E).

In another aspect, the present invention features a composition (e.g., amolecule, a monomer, a polymer, an article, etc.) including the formula(VIIIa), having the formula (VIIIa), or including a structure having theformula (VIIIa):

or a salt thereof (e.g., a cationic salt, such as a sodium salt) or aform thereof including a counter ion (e.g., an anion, such as anydescribed herein). In some embodiments, each of R^(AF) (e.g., R^(A) orR^(F)), R¹ , R³, Ar^(L), Ar^(M), q, a, m, n, L, and Ar* is,independently, any described herein. In some embodiments, each of m andn is, independently, an integer of from about 1 to 1000 (e.g., fromabout 1 to 500); L is a linking segment; and Ar* is a hydrophobicsegment. In further embodiments, at least one R¹ or Ar^(L) or Ar^(M) informula (VIIIa) includes R^(AF), R^(A), RF, R^(H), R^(S), R^(P), R^(C),or R^(E).

In yet another aspect, the present invention features a composition(e.g., a molecule, a monomer, a polymer, an article, etc.) including theformula (IX), having the formula (IX), or including a structure havingthe formula (IX):

or a salt thereof (e.g., a cationic salt, such as a sodium salt) or aform thereof including a counter ion (e.g., an anion, such as anydescribed herein). In some embodiments, each R^(H)* is, independently,R^(AF) or R^(H′)—R^(AF), where R^(AF) is a functional group including acationic moiety or a halo, and where R^(H′) is reacted reactive handle(e.g., any herein, where R^(H′) is selected from the group of anoptionally substituted alkyl (e.g., C₁₋₁₂ alkyl), optionally substitutedhaloalkyl (e.g., C₁₋₁₂ haloalkyl), optionally substituted perfluoroalkyl(e.g., C₁₋₁₂ perfluoroalkyl), optionally substituted heteroalkyl (e.g.,C₁₋₁₂ heteroalkyl), optionally substituted aryl (e.g., C₄₋₁₈ aryl),optionally substituted alkaryl (e.g., C₁₋₁₂ alk-C₄₋₁₈ aryl or C₁₋₆alk-C₄₋₁₈ aryl), optionally substituted arylalkoxy (e.g., C₄₋₁₈aryl-C₁₋₁₂ alkoxy or C₄₋₁₈ aryl-C₁₋₆ alkoxy), optionally substitutedaryloxy (e.g., C₄₋₁₈ aryloxy), optionally substituted aryloxycarbonyl(e.g., C₅₋₁₉ aryloxycarbonyl), optionally substituted aryloyl (e.g.,C₇₋₁₁ aryloyl or C₅₋₁₉ aryloyl), optionally substitutedarylcarbonylalkyl (e.g., C₄₋₁₈ arylcarbonyl-C₁₋₁₂ alkyl or C₄₋₁₈arylcarbonyl-C₁₋₆ alkyl), optionally substituted arylsulfonyl (e.g.,C₄₋₁₈ arylsulfoyl), or optionally substituted arylsulfonylalkyl (e.g.,C₄₋₁₈ arylsulfonyl-C₁₋₁₂ alkyl or C₄₋₁₈ arylsulfonyl-C₁₋₆ alkyl)). Insome embodiments, each of R^(AF) (e.g., R^(A) or R^(F)), R¹, R³, Ar^(L),Ar^(M), q, h*, and m is, independently, any described herein. In someembodiments, each h* is, independently, an integer of from 0 to 5,wherein at least one h* is not 0. In further embodiments, at least oneR¹ or Ar^(L) or Ar^(M) in formula (IX) includes R^(AF), R^(A), R^(F),R^(H), R^(S), R^(P), R^(C), or R^(E).

In some embodiments, the first composition is present in a polymericmembrane.

In any embodiment herein, L or L′ includes a covalent bond, optionallysubstituted C₁₋₁₂ alkylene, optionally substituted C₁₋₁₂ alkyleneoxy,optionally substituted C₁₋₁₂ heteroalkylene, optionally substitutedC₁₋₁₂ heteroalkyleneoxy, optionally substituted C₄₋₁₈ arylene,optionally substituted C₄₋₁₈ aryleneoxy, optionally substitutedpolyphenylene, or a structure of formula (II). In yet other embodiments,L or L′ includes a structure of formula (I) and Ar* (e.g., any subunitsdescribed herein for Ar*).

In any embodiment herein, Ar* or L or L′ includes a structure of formula(I), a sulfone subunit, an arylene sulfone subunit, an ether sulfonesubunit, an arylene ether subunit, a perfluoroalkyl subunit, or aperfluoroalkoxy subunit.

In any embodiment herein, each of Ar^(L), Ar^(M), and Ar* is optionallysubstituted phenylene, optionally substituted naphthylene, optionallysubstituted phenanthrylene, a sulfone subunit, an arylene sulfonesubunit, an ether sulfone subunit, an arylene ether subunit, aperfluoroalkyl subunit, a perfluoroalkoxy subunit, or any describedherein (e.g., any aryl group described herein). In further embodiments,the optional substitution is R^(AF), R^(A), R^(F), R^(H), R^(S), R^(P),R^(C), R^(E) or a label (e.g., fluorine or another NMR detectablelabel).

In any embodiment herein, m is less than n. In any embodiment herein, mis more than n.

In any embodiment herein, the cationic moiety includes an onium cation(e.g., an ammonium cation, a sulfonium cation, a phosphonium cation, anoxonium cation, a diazonium cation, or a halonium cation).

In any embodiment herein, the counter ion is an anion (e.g., a hydroxideanion (OH⁻), a halide anion (e.g., a chloride anion, a bromide anion, ora fluoride anion), or any described herein).

In any embodiment herein, R^(H) is a reactive handle. In someembodiments, each R^(H) is, independently, H, optionally substitutedalkyl (e.g., C₁₋₁₂ alkyl), optionally substituted haloalkyl (e.g., C₁₋₁₂haloalkyl), optionally substituted perfluoroalkyl (e.g., C₁₋₁₂perfluoroalkyl), optionally substituted heteroalkyl (e.g., C₁₋₁₂heteroalkyl), halo, optionally substituted aryl (e.g., C₄₋₁₈ aryl),optionally substituted alkaryl (e.g., C₁₋₁₂ alk-C₄₋₁₈ aryl or C₁₋₆alk-C₄₋₁₈ aryl), optionally substituted arylalkoxy (e.g., C₄₋₁₈aryl-C₁₋₁₂ alkoxy or C₄₋₁₈ aryl-C₁₋₆ alkoxy), optionally substitutedaryloxy (e.g., C₄₋₁₈ aryloxy), optionally substituted aryloxycarbonyl(e.g., C₅₋₁₉ aryloxycarbonyl), optionally substituted aryloyl (e.g.,C₇₋₁₁ aryloyl or C₅₋₁₉ aryloyl), optionally substitutedarylcarbonylalkyl (e.g., C₄₋₁₈ arylcarbonyl-C₁₋₁₂ alkyl or C₄₋₁₈arylcarbonyl-C₁₋₆ alkyl), optionally substituted arylsulfonyl (e.g.,C₄₋₁₈ arylsulfoyl), or optionally substituted arylsulfonylalkyl (e.g.,C₄₋₁₈ arylsulfonyl-C₁₋₁₂ alkyl or C₄₋₁₈ arylsulfonyl-C₁₋₆ alkyl). Inother embodiments, R^(H) is -L^(H)-Ar^(H) or R^(H) is —L^(H)-Ak^(H)(e.g., Ar^(H) is an optionally substituted aryl (e.g., substituted withone or more substituents selected from the group of halo, cyano,optionally substituted haloalkyl, optionally substituted perfluoroalkyl,optionally substituted nitroalkyl, and optionally substituted alkyl);Ak^(H) is an optionally substituted alkyl or optionally substitutedheteroalkyl (e.g., substituted with one or more substituents selectedfrom the group of halo, cyano, optionally substituted haloalkyl,optionally substituted perfluoroalkyl, optionally substitutednitroalkyl, and optionally substituted alkyl); and L^(H) is a linker,such as any described herein for L^(A)).

In any embodiment herein, R^(H) is R^(AF), R^(A), or R^(F); and h can bea.

In any embodiment herein, R^(H1) is R^(A1) or R^(F1).

In any embodiment herein, R^(H) can be reacted with a reactant toprovide an R^(AF), R^(A), or R^(F) group.

In any embodiment herein, R^(H1) can be reacted with a reactant toprovide R^(A1) or R^(F1).

Definitions

As used herein, the term “about” means +/−10% of any recited value. Asused herein, this term modifies any recited value, range of values, orendpoints of one or more ranges.

The term “acyl,” or “alkanoyl,” as used interchangeably herein,represent an alkyl group, as defined herein, or hydrogen attached to theparent molecular group through a carbonyl group, as defined herein. Thisgroup is exemplified by formyl, acetyl, propionyl, butanoyl, and thelike. The alkanoyl group can be substituted or unsubstituted. Forexample, the alkanoyl group can be substituted with one or moresubstitution groups, as described herein for alkyl. In some embodiments,the unsubstituted acyl group is a C₂₋₇ acyl or alkanoyl group.

By “alkaryl” is meant an aryl group, as defined herein, attached to theparent molecular group through an alkylene group, as defined herein.Similarly, by the term “alkheteroaryl” is meant a heteroaryl group, asdefined herein, attached to the parent molecular group through analkylene group. Other groups preceded by the prefix “alk-” are definedin the same manner. The alkaryl group can be substituted orunsubstituted. For example, the alkaryl group can be substituted withone or more substitution groups, as described herein for alkyl and/oraryl. Exemplary unsubstituted alkaryl groups are of from 7 to 16 carbons(C₇₋₁₆ alkaryl), as well as those having an alkylene group with 1 to 6carbons and an aryl group with 4 to 18 carbons (i.e., C₁₋₆ alk-C₄₋₁₈aryl).

By “alkcycloalkyl” is meant a cycloalkyl group, as defined herein,attached to the parent molecular group through an alkylene group, asdefined herein. The alkcycloalkyl group can be substituted orunsubstituted. For example, the alkcycloalkyl group can be substitutedwith one or more substitution groups, as described herein for alkyl.

By “alkenyl” is meant an optionally substituted C₂₋₂₄ alkyl group havingone or more double bonds. The alkenyl group can be cyclic (e.g., C₃₋₂₄cycloalkenyl) or acyclic. The alkenyl group can also be substituted orunsubstituted. For example, the alkenyl group can be substituted withone or more substitution groups, as described herein for alkyl.

By “alkheterocyclyl” represents a heterocyclyl group, as defined herein,attached to the parent molecular group through an alkylene group, asdefined herein. Exemplary unsubstituted alkheterocyclyl groups are offrom 2 to 14 carbons.

By “alkoxy” is meant —OR, where R is an optionally substituted alkylgroup, as described herein. Exemplary alkoxy groups include methoxy,ethoxy, butoxy, trihaloalkoxy, such as trifluoromethoxy, etc. The alkoxygroup can be substituted or unsubstituted. For example, the alkoxy groupcan be substituted with one or more substitution groups, as describedherein for alkyl. Exemplary unsubstituted alkoxy groups include C₁₋₃,C₁₋₆, C₁₋₁₂, C₁₋₁₆, C₁₋₁₈, C₁₋₂₀, or C₁₋₂₄ alkoxy groups.

By “alkoxyalkyl” is meant an alkyl group, as defined herein, which issubstituted with an alkoxy group, as defined herein. Exemplaryunsubstituted alkoxyalkyl groups include between 2 to 12 carbons (C₂₋₁₂alkoxyalkyl), as well as those having an alkyl group with 1 to 6 carbonsand an alkoxy group with 1 to 6 carbons (i.e., C₁₋₆ alkoxy-C₁₋₆ alkyl).

By “alkoxycarbonyl” is meant an alkoxy group, as defined herein, that isattached to the parent molecular group through a carbonyl group. In someembodiments, an unsubstituted alkoxycarbonyl group is a C₂₋₇alkoxycarbonyl group.

By “alkyl” and the prefix “alk” is meant a branched or unbranchedsaturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl,n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and thelike. The alkyl group can be cyclic (e.g., C₃₋₂₄ cycloalkyl) or acyclic.The alkyl group can be branched or unbranched. The alkyl group can alsobe substituted or unsubstituted. For example, the alkyl group can besubstituted with one, two, three or, in the case of alkyl groups of twocarbons or more, four substituents independently selected from the groupconsisting of: (1) C₁₋₆ alkoxy; (2) C₁₋₆ alkylsulfinyl; (3) C₁₋₆alkylsulfonyl; (4) amino; (5) aryl; (6) arylalkoxy; (7) aryloyl; (8)azido; (9) cyano; (10) carboxyaldehyde; (11) C₃₋₈ cycloalkyl; (12) halo;(13) heterocyclyl; (14) heterocyclyloxy; (15) heterocyclyloyl; (16)hydroxyl; (17) N-protected amino; (18) nitro; (19) oxo; (20) C₃₋₈spirocyclyl; (21) C₁₋₆ thioalkoxy; (22) thiol; (23) —CO₂R^(A), whereR^(A) is selected from the group consisting of (a) hydrogen, (b) C₁₋₆alkyl, (c) C₄₋₁₈ aryl, and (d) C₁₋₆ alk-C₄₋₁₈ aryl; (24)—C(O)NR^(B)R^(C), where each of R^(B) and R^(C) is, independently,selected from the group consisting of (a) hydrogen, (b) C₁₋₆ alkyl, (c)C₄₋₁₈ aryl, and (d) C₁₋₆ alk-C₄₋₁₈ aryl; (25) —SO₂R^(D), where R^(D) isselected from the group consisting of (a) C₁₋₆ alkyl, (b) C₄₋₁₈ aryl,and (c) C₁₋₆ alk-C₄₋₁₈ aryl; (26) —SO₂NR^(E)R^(F), where each of R^(E)and R^(F) is, independently, selected from the group consisting of (a)hydrogen, (b) C₁₋₆ alkyl, (c) C₄₋₁₈ aryl, and (d) C₁₋₆ alk-C₄₋₁₈ aryl;and (27) —NR^(G)R^(H), where each of R^(G) and R^(H) is, independently,selected from the group consisting of (a) hydrogen, (b) an N-protectinggroup, (c) C₁₋₆ alkyl, (d) C₂₋₆ alkenyl, (e) C₂₋₆ alkenyl, (f) C₄₋₁₈aryl, (g) C₁₋₆ alk-C₄₋₁₈ aryl, (h) C₃₋₈ cycloalkyl, and (i) C₁₋₆alk-C₃₋₈ cycloalkyl, wherein in one embodiment no two groups are boundto the nitrogen atom through a carbonyl group or a sulfonyl group. Thealkyl group can be a primary, secondary, or tertiary alkyl groupsubstituted with one or more substituents (e.g., one or more halo oralkoxy). In some embodiments, the unsubstituted alkyl group is a C₁₋₃,C₁₋₆, C₁₋₁₂, C₁₋₁₆, C₁₋₁₈, C₁₋₂₀, or C₁₋₂₄ alkyl group.

By “alkylene” is meant a bivalent form of an alkyl group, as describedherein. Exemplary alkylene groups include methylene, ethylene,propylene, butylene, etc. In some embodiments, the alkylene group is aC₁₋₃, C₁₋₆, C₁₋₁₂, C₁₋₁₆, C₁₋₁₈, C₁₋₂₀, C₁₋₂₄, C₂₋₃, C₂₋₆, C₂₋₁₂, C₂₋₁₆,C₂₋₁₈, C₂₋₂₀, or C₂₋₂₄ alkylene group. The alkylene group can bebranched or unbranched. The alkylene group can also be substituted orunsubstituted. For example, the alkylene group can be substituted withone or more substitution groups, as described herein for alkyl.

By “alkyleneoxy” is meant an alkylene group, as defined herein, attachedto the parent molecular group through an oxygen atom.

By “alkylsulfate” is meant an alkyl group, as defined herein, attachedto the parent molecular group through an —O—(SO₂)— group. An exemplaryalkylsulfate group is —O—SO₂-Ak, where each Ak is, independently,optionally substituted alkyl.

By “alkylsulfinyl” is meant an alkyl group, as defined herein, attachedto the parent molecular group through an group. In some embodiments, theunsubstituted alkylsulfinyl group is a C₁₋₆ or C₁₋₁₂ alkylsulfinylgroup.

By “alkylsulfinylalkyl” is meant an alkyl group, as defined herein,substituted by an alkylsulfinyl group. In some embodiments, theunsubstituted alkylsulfinylalkyl group is a C₂₋₁₂ or C₂₋₂₄alkylsulfinylalkyl group (e.g., C₁₋₆ alkylsulfinyl-C₁₋₆ alkyl or C₁₋₁₂alkylsulfinyl-C₁₋₁₂ alkyl).

By “alkylsulfonyl” is meant an alkyl group, as defined herein, attachedto the parent molecular group through an group. In some embodiments, theunsubstituted alkylsulfonyl group is a C₁₋₆ or C₁₋₁₂ alkylsulfonylgroup. In other embodiments, the alkylsulfonyl group is —SO₂—R^(S1),where R^(S1) is an optionally substituted C₁₋₁₂ alkyl (e.g., asdescribed herein, including optionally substituted C₁₋₁₂ haloalkyl orperfluoroalkyl).

By “alkylsulfonylalkyl” is meant an alkyl group, as defined herein,substituted by an alkylsulfonyl group. In some embodiments, theunsubstituted alkylsulfonylalkyl group is a C₂₋₁₂ or C₂₋₂₄alkylsulfonylalkyl group (e.g., C₁₋₆ alkylsulfonyl-C₁₋₆ alkyl or C₁₋₁₂alkylsulfonyl-C₁₋₁₂ alkyl). An exemplary alkylsulfonylalkyl group is—C—(SO₂-Ak)₃, where each Ak is, independently, optionally substitutedalkyl.

By “alkylsulfonylamide” is meant an amino group, as defined herein,substituted by an alkylsulfonyl group. In some embodiments, theunsubstituted alkylsulfonylamide group is —NR^(N1)R^(N2), in which eachof R^(N1) and R^(N2) is, independently, H, C₁₋₁₂ alkyl, or C₁₋₂₄alkylsulfonyl group (e.g., C₁₋₆ alkylsulfonyl or C₁₋₁₂ alkylsulfonyl),where at least one of R^(N1) and R^(N2) includes a sulfonyl group. Anexemplary alkylsulfonylamide group is —N—(SO₂-Ak)₂ or —N(Ak)(SO₂-Ak),where each Ak is, independently, optionally substituted alkyl.

By “alkynyl” is meant an optionally substituted C₂₋₂₄ alkyl group havingone or more triple bonds. The alkynyl group can be cyclic or acyclic andis exemplified by ethynyl, 1-propynyl, and the like. The alkynyl groupcan also be substituted or unsubstituted. For example, the alkynyl groupcan be substituted with one or more substitution groups, as describedherein for alkyl.

By “amidino” is meant —C(NR^(N3))NR^(N1)R^(N2), where each of R^(N1),R^(N2), and R^(N3) is, independently, H or optionally substituted alkyl,or R^(N1) and R^(N2), taken together with the nitrogen atom to whicheach are attached, form a heterocyclyl group, as defined herein.

By “amino” is meant —C(O)NR^(N1)R^(N2), where each of R^(N1) and R^(N2)is, independently, H or optionally substituted alkyl, or R^(N1) andR^(N2), taken together with the nitrogen atom to which each areattached, form a heterocyclyl group, as defined herein.

By “amino” is meant —NR^(N1)R^(N2), where each of R^(N1) and R^(N2) is,independently, H or optionally substituted alkyl, or R^(N1) and R^(N2),taken together with the nitrogen atom to which each are attached, form aheterocyclyl group, as defined herein.

By “aminoalkyl” is meant an alkyl group, as defined herein, substitutedby an amino group, as defined herein.

By “ammonium” is meant a group including a protonated nitrogen atom N⁺.Exemplary ammonium groups include —N⁺R^(N1)R^(N2)R^(N3) where each ofR^(N1), R^(N2), and R^(N3) is, independently, H, optionally substitutedalkyl, optionally substituted aryl, or optionally substituted alkaryl;or R^(N1) and R^(N2), taken together with the nitrogen atom to whicheach are attached, form a heterocycle; or R^(N1) and R^(N2), takentogether, form an optionally substituted alkylene or heteroalkylene(e.g., as described herein).

By “anion” is meant a monoatomic or polyatomic species having one ormore elementary charges of the electron. Exemplary, non-limiting anionsinclude a halide (e.g., F⁻, Cl⁻, Br⁻, or I⁻), a hydroxide (e.g., OH⁻), aborate (e.g., tetrafluoroborate (BF₄ ⁻), a carbonate (e.g., CO₃ ²⁻ orHCO₃ ⁻), or a sulfate (e.g., SO₄ ²⁻).

By “aryl” is meant a group that contains any carbon-based aromatic groupincluding, but not limited to, benzyl, naphthalene, phenyl, biphenyl,phenoxybenzene, and the like. The term “aryl” also includes“heteroaryl,” which is defined as a group that contains an aromaticgroup that has at least one heteroatom incorporated within the ring ofthe aromatic group. Examples of heteroatoms include, but are not limitedto, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term“non-heteroaryl,” which is also included in the term “aryl,” defines agroup that contains an aromatic group that does not contain aheteroatom. The aryl group can be substituted or unsubstituted. The arylgroup can be substituted with one, two, three, four, or fivesubstituents independently selected from the group consisting of: (1)C₁₋₆ alkanoyl; (2) C₁₋₆ alkyl; (3) C₁₋₆ alkoxy; (4) C₁₋₆ alkoxy-C₁₋₆alkyl; (5) C₁₋₆ alkylsulfinyl; (6) C₁₋₆ alkylsulfinyl-C₁₋₆ alkyl; (7)C₁₋₆ alkylsulfonyl; (8) C₁₋₆ alkylsulfonyl-C₁₋₆ alkyl; (9) aryl; (10)amino; (11) C₁₋₆ aminoalkyl; (12) heteroaryl; (13) C₁₋₆ alk-C₄₋₁₈ aryl;(14) aryloyl; azido; (16) cyano; (17) C₁₋₆ azidoalkyl; (18)carboxyaldehyde; (19) carboxyaldehyde-C₁₋₆ alkyl; (20) C₃₋₈ cycloalkyl;(21) C₁₋₆ alk-C₃₋₈ cycloalkyl; (22) halo; (23) C₁₋₆ haloalkyl; (24)heterocyclyl; (25) heterocyclyloxy; (26) heterocyclyloyl; (27) hydroxyl;(28) C₁₋₆ hydroxyalkyl; (29) nitro; (30) C₁₋₆ nitroalkyl; (31)N-protected amino; (32) N-protected amino-C₁₋₆ alkyl; (33) oxo; (34)C₁₋₆ thioalkoxy; (35) thio-C₁₋₆ alkoxy-C₁₋₆ alkyl; (36)—(CH₂)_(r)CO₂R^(A), where r is an integer of from zero to four, andR^(A) is selected from the group consisting of (a) hydrogen, (b) C₁₋₆alkyl, (c) C₄₋₁₈ aryl, and (d) aryl; (37) —(CH₂)_(r)CONR^(B)R^(C), wherer is an integer of from zero to four and where each R^(B) and R^(C) isindependently selected from the group consisting of (a) hydrogen, (b)C₁₋₆ alkyl, (c) C₄₋₁₈ aryl, and (d) C₁₋₆ alk-C₄₋₁₈ aryl; (38)—(CH₂)_(r)SO₂R^(D), where r is an integer of from zero to four and whereR^(D) is selected from the group consisting of (a) C₁₋₆ alkyl, (b) C₄₋₁₈aryl, and (c) C₁₋₆ alk-C₄₋₁₈ aryl; (39) —(CH₂)_(r)SO₂NR^(E)R^(F), wherer is an integer of from zero to four and where each of R^(E) and R^(F)is, independently, selected from the group consisting of (a) hydrogen,(b) C₁₋₆ alkyl, (c) C₄₋₁₈ aryl, and (d) C₁₋₆ alk-C₄₋₁₈ aryl; (40)—(CH₂)_(r)NR^(G)R^(H), where r is an integer of from zero to four andwhere each of R^(G) and R^(H) is, independently, selected from the groupconsisting of (a) hydrogen, (b) an N-protecting group, (c) C₁₋₆ alkyl,(d) C₂₋₆ alkenyl, (e) C₂₋₆ alkynyl, (f) C₄₋₁₈ aryl, (g) C₁₋₆ alk-C₄₋₁₈aryl, (h) C₃₋₈ cycloalkyl, and (i) C₁₋₆ alk-C₃₋₈ cycloalkyl, wherein inone embodiment no two groups are bound to the nitrogen atom through acarbonyl group or a sulfonyl group; (41) thiol; (42) perfluoroalkyl;(43) perfluoroalkoxy; (44) aryloxy; (45) cycloalkoxy; (46)cycloalkylalkoxy; and (47) arylalkoxy. In particular embodiments, anunsubstituted aryl group is a C₄₋₁₈, C₄₋₁₄, C₄₋₁₂, C₄₋₁₀, C₆₋₁₈, C₆₋₁₄,C₆₋₁₂, or C₆₋₁₀ aryl group.

By “arylcarbonylalkyl” is meant an alkyl group, as defined herein,substituted by an aryloyl group, as defined herein. In some embodiments,the arylcarbonylalkyl group is Ar—C(O)-Ak-, in which Ar is an optionallysubstituted aryl group and Ak is an optionally substituted alkyl oroptionally substituted alkylene group. In particular embodiments, anunsubstituted arylcarbonylalkyl group is a C₄₋₂₀ aryl-C(O)—C₁₋₁₂ alkylgroup or a C₄₋₁₂ aryl-C(O)—C₁₋₆ alkyl group or a C₄₋₁₈ aryl-C(O)—C₁₋₆alkyl group.

By “arylene” is meant a bivalent form of an aryl group, as describedherein. Exemplary arylene groups include phenylene, naphthylene,biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene,or phenanthrylene. in some embodiments, the arylene group is a C₄₋₁₈,C₄₋₁₄, C₄₋₁₂, C₄₋₁₀, C₆₋₁₈, C₆₋₁₄, C₆₋₁₂, or C₆₋₁₀ arylene group. Thearylene group can be branched or unbranched. The arylene group can alsobe substituted or unsubstituted. For example, the arylene group can besubstituted with one or more substitution groups, as described hereinfor aryl.

By “aryleneoxy” is meant an arylene group, as defined herein, attachedto the parent molecular group through an oxygen atom.

By “arylalkoxy” is meant an alkaryl group, as defined herein, attachedto the parent molecular group through an oxygen atom.

By “aryloxy” is meant —OR, where R is an optionally substituted arylgroup, as described herein. In some embodiments, an unsubstitutedaryloxy group is a C₄₋₁₈ or C₆₋₁₈ aryloxy group.

By “aryloxycarbonyl” is meant an aryloxy group, as defined herein, thatis attached to the parent molecular group through a carbonyl group. Insome embodiments, an unsubstituted aryloxycarbonyl group is a C₅₋₁₉aryloxycarbonyl group.

By “aryloyl” is meant an aryl group that is attached to the parentmolecular group through a carbonyl group. In some embodiments, anunsubstituted aryloyl group is a C₇₋₁₁ aryloyl or C₅₋₁₉ aryloyl group.

By “arylsulfonyl” is meant an aryl group, as defined herein, attached tothe parent molecular group through an —SO₂— group.

By “arylsulfonylalkyl” is meant an alkyl group, as defined herein,substituted by an arylsulfonyl group. In some embodiments, thearylcarbonylalkyl group is Ar—SO₂-Ak-, in which Ar is an optionallysubstituted aryl group and Ak is an optionally substituted alkyl oroptionally substituted alkylene group. In particular embodiments, theunsubstituted arylsulfonylalkyl group is a C₄₋₂₀ aryl-SO₂—C₁₋₁₂ alkylgroup or a C₄₋₁₂ aryl-SO₂—C₁₋₆ alkyl group or a C₄₋₁₈ aryl-SO₂—C₁₋₆alkyl group.

By “azido” is meant an —N₃ group.

By “azo” is meant an —N═N— group.

By “azidoalkyl” is meant an azido group attached to the parent moleculargroup through an alkyl group, as defined herein.

By “carbonyl” is meant a —C(O)— group, which can also be represented as>C═O.

By “carboxyaldehyde” is meant a —C(O)H group.

By “carboxyaldehydealkyl” is meant a carboxyaldehyde group, as definedherein, attached to the parent molecular group through an alkylenegroup, as defined herein.

By “carboxyl” is meant a —CO₂H group.

By “cyano” is meant a —CN group.

By “cycloalkyl” is meant a monovalent saturated or unsaturatednon-aromatic cyclic hydrocarbon group of from three to eight carbons,unless otherwise specified, and is exemplified by cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyland the like. The cycloalkyl group can also be substituted orunsubstituted. For example, the cycloalkyl group can be substituted withone or more groups including those described herein for alkyl.

By “cycloalkoxy” is meant a cycloalkyl group, as defined herein,attached to the parent molecular group through an oxygen atom.

By “diazonium” is meant a group including

By “dithiocarboxyamino” is meant —NR^(N1)C(S)SR^(S1), where each ofR^(N1) and R^(S1) is, independently, H or optionally substituted alkyl,or R^(N1) and R^(S1), taken together with the nitrogen atom to whicheach are attached, form a heterocyclyl group, as defined herein.

By “halo” is meant F, Cl, Br, or I.

By “haloalkyl” is meant an alkyl group, as defined herein, substitutedwith one or more halo.

By “halonium” is meant a group including —X⁺, where X is halo as definedherein. Exemplary halonium groups include an iodonium group (e.g., —I⁺),a bromonium group (e.g., —Br⁺), a chloronium group (e.g., —Cl⁺), or afluoronium group (e.g., —F⁺).

By “heteroalkyl” is meant an alkyl group, as defined herein, containingone, two, three, or four non-carbon heteroatoms (e.g., independentlyselected from the group consisting of nitrogen, oxygen, phosphorous,sulfur, or halo).

By “heteroalkylene” is meant a divalent form of an alkylene group, asdefined herein, containing one, two, three, or four non-carbonheteroatoms (e.g., independently selected from the group consisting ofnitrogen, oxygen, phosphorous, sulfur, or halo).

By “heteroalkyleneoxy” is meant a heteroalkylene group, as definedherein, attached to the parent molecular group through an oxygen atom.

By “heteroaryl” is meant a subset of heterocyclyl groups, as definedherein, which are aromatic, i.e., they contain 4n+2 pi electrons withinthe mono- or multicyclic ring system.

By “heterocyclyl” is meant a 5-, 6- or 7-membered ring, unless otherwisespecified, containing one, two, three, or four non-carbon heteroatoms(e.g., independently selected from the group consisting of nitrogen,oxygen, phosphorous, sulfur, or halo). The 5-membered ling has zero totwo double bonds and the 6- and 7-membered rings have zero to threedouble bonds. The term “heterocyclyl” also includes bicyclic, tricyclicand tetracyclic groups in which any of the above heterocyclic rings isfused to one, two, or three rings independently selected from the groupconsisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, acyclopentane ring, a cyclopentene ring, and another monocyclicheterocyclic ring, such as indolyl, quinolyl, isoquinolyl,tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclicsinclude thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl,aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl,pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl,imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl,piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl,isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl,thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl,isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl,thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl,tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl,tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl,dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl,dihydropyranyl, dithiazolyl, benzofuranyl, benzothienyl, and the like.

By “heterocyclyloxy” is meant a heterocyclyl group, as defined herein,attached to the parent molecular group through an oxygen atom.

By “heterocyclyloyl” is meant a heterocyclyl group, as defined herein,attached to the parent molecular group through a carbonyl group.

By “hydroxyl” is meant —OH.

By “hydroxyalkyl” is meant an alkyl group, as defined herein,substituted by one to three hydroxyl groups, with the proviso that nomore than one hydroxyl group may be attached to a single carbon atom ofthe alkyl group and is exemplified by hydroxymethyl, dihydroxypropyl,and the like.

By “imine” is meant —CR^(L1)═N—, where R^(L1) is H or optionallysubstituted alkyl.

By “imino” is meant —NH—.

By “nitrilo” is meant —N<. Exemplary nitrilo groups include —NR^(L3)—,where R^(L3) is H, optionally substituted alkyl, optionally substitutedhaloalkyl, optionally substituted alkoxy, optionally substitutedalkaryl, optionally substituted aryl, or halo.

By “nitro” is meant an —NO₂ group.

By “nitroalkyl” is meant an alkyl group, as defined herein, substitutedby one to three nitro groups.

By “nitroso” is meant an —NO group.

By “oxo” is meant an ═O group.

By “oxonium” is meant a group including a protonated oxygen atom O⁺.Exemplary oxonium groups include —O⁺R^(O1)R^(O2), where each of R^(O1)and R^(O2) is, independently, H, optionally substituted alkyl,optionally substituted alkenyl, optionally substituted aryl, oroptionally substituted alkaryl; or wherein R^(O1) and R^(O2), takentogether, form an optionally substituted alkylene or heteroalkylene(e.g., as described herein).

By “oxy” is meant —O—.

By “perfluoroalkyl” is meant an alkyl group, as defined herein, havingeach hydrogen atom substituted with a fluorine atom. Exemplaryperfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, etc.

By “perfluoroalkylene” is meant an alkylene group, as defined herein,having each hydrogen atom substituted with a fluorine atom. Exemplaryperfluoroalkylene groups include difluoromethylene, tetrafluoroethylene,etc.

By “perfluoroalkyleneoxy” is meant a perfluoroalkylene group, as definedherein, having an oxy group attached to either end of theperfluoroalkylene group. Exemplary perfluoroalkylene groups include,e.g., —OC_(f)F_(2f) — or —C_(f)F_(2f)O—, where f is an integer fromabout 1 to 5, and 2f is an integer that is 2 times f (e.g.,difluoromethyleneoxy, tetrafluoroethyleneoxy, etc.).

By “perfluoroalkoxy” is meant an alkoxy group, as defined herein, havingeach hydrogen atom substituted with a fluorine atom.

By “phosphine” is meant a —PR^(L3)— group, where R^(L3) is H oroptionally substituted alkyl.

By “phosphonium” is meant a group including a protonated phosphorousatom P⁺. Exemplary phosphonium groups include —P⁺R^(P1)R^(P2)R^(R3),where each of R^(P1), R^(P2), and R^(P3) is, independently, H,optionally substituted alkyl, optionally substituted alkenyl, optionallysubstituted aryl, or optionally substituted alkaryl; or wherein two ofR^(P1), R^(P2), and R^(P3), taken together, form an optionallysubstituted alkylene or heteroalkylene (e.g., as described herein).

By “phosphono” is meant a —P(O)(OH)₂ group.

By “phosphonoyl” is meant a —P(O)H— group.

By “phosphoric ester” is meant a —O—PO(OH)₂ group.

By “phosphoryl” is meant a —P(O)<group.

By “protecting group” is meant any group intended to protect a reactivegroup against undesirable synthetic reactions. Commonly used protectinggroups are disclosed in “Greene's Protective Groups in OrganicSynthesis,” John Wiley & Sons, New York, 2007 (4th ed., eds. P. G. M.Wuts and T. W. Greene), which is incorporated herein by reference.O-protecting groups include an optionally substituted alkyl group (e.g.,forming an ether with reactive group O), such as methyl, methoxymethyl,methylthiomethyl, benzoyloxymethyl, t-butoxymethyl, etc.; an optionallysubstituted alkanoyl group (e.g., forming an ester with the reactivegroup O), such as formyl, acetyl, chloroacetyl, fluoroacetyl (e.g.,perfluoroacetyl), methoxyacetyl, pivaloyl, t-butylacetyl, phenoxyacetyl,etc.; an optionally substituted aryloyl group (e.g., forming an esterwith the reactive group O), such as —C(O)—Ar, including benzoyl; anoptionally substituted alkylsulfonyl group (e.g., forming analkylsulfonate with reactive group O), such as —SO₂—R^(S1), where R^(S1)is optionally substituted C₁₋₁₂ alkyl, such as mesyl or benzylsulfonyl,an optionally substituted arylsulfonyl group (e.g., forming anarylsulfonate with reactive group O), such as —SO₂—R^(S4), where R^(S4)is optionally substituted C₄₋₁₈ aryl, such as tosyl or phenylsulfonyl;an optionally substituted alkoxycarbonyl or aryl oxycarbonyl group(e.g., forming a carbonate with reactive group O), such as—C(O)—OR^(T1), where R^(T1) is optionally substituted C₁₋₁₂ alkyl oroptionally substituted C₄₋₁₈ aryl, such as methoxycarbonyl,methoxymethylcarbonyl, t-butyloxycarbonyl (Boc), or benzyloxycarbonyl(Cbz); or an optionally substituted silyl group (e.g., forming a silylether with reactive group O), such as —Si—(R^(T2))₃, where each R^(T2)is, independently, optionally substituted C₁₋₁₂ alkyl or optionallysubstituted C₄₋₁₈ aryl, such as trimethylsilyl, t-butyldimethylsilyl, ort-butyldiphenylsilyl. N-protecting groups include, e.g., formyl, acetyl,benzoyl, pivaloyl, t-butylacetyl, alanyl, phenylsulfonyl, benzyl, Boc,and Cbz. Such protecting groups can employ any useful agent to cleavethe protecting group, thereby restoring the reactivity of theunprotected reactive group.

By “salt” is meant an ionic form of a compound or structure (e.g., anyformulas, compounds, or compositions described herein), which includes acation or anion compound to form an electrically neutral compound orstructure. Salts are well known in the art. For example, non-toxic saltsare described in Berge S M et al., “Pharmaceutical salts,” J. Pharm.Sci. 1977 January; 66(1):1-19; and in “Handbook of Pharmaceutical Salts:Properties, Selection, and Use,” Wiley-VCH, April 2011 (2nd rev. ed.,eds. P. H. Stahl and C. G. Wermuth. The salts can be prepared in situduring the final isolation and purification of the compounds of theinvention or separately by reacting the free base group with a suitableorganic acid (thereby producing an anionic salt) or by reacting the acidgroup with a suitable metal or organic salt (thereby producing acationic salt). Representative anionic salts include acetate, adipate,alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate,bisulfate, bitartrate, borate, bromide, butyrate, camphorate,camphorsulfonate, chloride, citrate, cyclopentanepropionate,digluconate, dihydrochloride, diphosphate, dodecylsulfate, edetate,ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate,glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide,hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate,iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate,malonate, mandelate, mesylate, methanesulfonate, methylbromide,methylnitrate, methyl sulfate, mucate, 2-naphthalenesulfonate,nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate,persulfate, 3-phenylpropionate, phosphate, picrate, pivalate,polygalacturonate, propionate, salicylate, stearate, subacetate,succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate,triethiodide, toluenesulfonate, undecanoate, valerate salts, and thelike. Representative cationic salts include metal salts, such as alkalior alkaline earth salts, e.g., barium, calcium (e.g., calcium edetate),lithium, magnesium, potassium, sodium, and the like; other metal salts,such as aluminum, bismuth, iron, and zinc; as well as nontoxic ammonium,quaternary ammonium, and amine cations, including, but not limited toammonium, tetramethylammonium, tetraethylammonium, methylamine,dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium,and the like. Other cationic salts include organic salts, such aschloroprocaine, choline, dibenzylethylenediamine, diethanolamine,ethylenediamine, methylglucamine, and procaine. Yet other salts includeammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium,benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium,pyridinium, etc., as well as other cationic groups described herein(e.g., optionally substituted isoxazolium, optionally substitutedoxazolium, optionally substituted thiazolium, optionally substitutedpyrrolium, optionally substituted (uranium, optionally substitutedthiophenium, optionally substituted imidazolium, optionally substitutedpyrazolium, optionally substituted isothiazolium, optionally substitutedtriazolium, optionally substituted tetrazolium, optionally substitutedfurazanium, optionally substituted pyridinium, optionally substitutedpyrimidinium, optionally substituted pyrazinium, optionally substitutedtriazinium, optionally substituted tetrazinium, optionally substitutedpyridazinium, optionally substituted oxazinium, optionally substitutedpyrrolidinium, optionally substituted pyrazolidinium, optionallysubstituted imidazolinium, optionally substituted isoxazolidinium,optionally substituted oxazolidinium, optionally substitutedpiperazinium, optionally substituted piperidinium, optionallysubstituted morpholinium, optionally substituted azepanium, optionallysubstituted azepinium, optionally substituted indolium, optionallysubstituted isoindolium, optionally substituted indolizinium, optionallysubstituted indazolium, optionally substituted benzimidazolium,optionally substituted isoquinolinum, optionally substitutedquinolizinium, optionally substituted dehydroquinolizinium, optionallysubstituted quinolinium, optionally substituted isoindolinium,optionally substituted benzimidazolinium, and optionally substitutedpurinium).

By “spirocyclyl” is meant an alkylene diradical, both ends of which arebonded to the same carbon atom of the parent group to form a spirocyclylgroup and also a heteroalkylene diradical both ends of which are bondedto the same atom.

By “sulfinyl” is meant an —S(O)— group.

By “sulfo” is meant an —S(O)₂OH group.

By “sulfone” is meant R′—S(O)₂—R″, where R′ and R″ is an organic moiety.Exemplary groups for R′ and R″ include, independently, optionallysubstituted alkyl, alkenyl, alkynyl, alkaryl, alkheterocyclyl,alkcycloalkyl, alkanoyl, alkoxy, alkoxyalkyl, alkoxycarbonyl,alkylsulfinyl, alkylsulfonyl, alkylsulfinylalkyl, alkylsulfonylalkyl,aminoalkyl, aryl, arylalkoxy, aryloxy, aryloxycarbonyl, aryloyl,arylsulfonyl, arylsulfonylalkyl, azidoalkyl, carboxyaldehyde,carboxyaldehydealkyl, carboxyl, cyano, cycloalkyl, cycloalkoxy,haloalkyl, heteroaryl, heterocyclyl, heterocyclyloxy, heterocyclyloyl,hydroxyalkyl, nitroalkyl, perfluoroalkyl, perfluoroalkoxy, spirocyclyl,thioalkaryl, thioalkheterocyclyl, or thioalkoxy, as defined herein. Thesulfone can be unsubstituted or substituted. For example, the sulfonecan be substituted with one or more substitution groups, as describedherein for alkyl and/or aryl.

By “sulfonyl” is meant an —S(O)₂— group.

By “sulfonamide” is meant an —S(O)₂—NR^(L3)— or an —NR^(L3)—S(O)₂—group, in which R^(L3) is any useful moiety. Exemplary R^(L3) groupsinclude H, optionally substituted alkyl, optionally substitutedhaloalkyl, optionally substituted alkoxy, optionally substitutedalkaryl, optionally substituted aryl, or halo.

By “sulfonium” is meant a group including a protonated sulfur atom S⁺.Exemplary sulfonium groups include —S⁺R^(S1)R^(S2), where each of R^(S1)and R^(S2) is, independently, H, optionally substituted alkyl,optionally substituted aryl, optionally substituted alkaryl, oroptionally substituted alkenyl; or R^(S1) and R^(S2) taken together withthe sulfur atom to which each are attached, form a heterocycle; orR^(S1) and R^(S2), taken together, form an optionally substitutedalkylene or heteroalkylene (e.g., as described herein).

By “thioalkaryl” is meant a thioalkoxy group, as defined herein,substituted with an aryl group, as defined herein.

By “thioalkheterocyclyl” is meant a thioalkoxy group, as defined herein,substituted with a heterocyclyl group, as defined herein.

By “thioalkoxy” is meant an alkyl group, as defined herein, attached tothe parent molecular group through a sulfur atom. Exemplaryunsubstituted thioalkoxy groups include C₁₋₆ thioalkoxy.

By “thioamido” is meant —C(S)NR^(N1)R^(N2), where each of R^(N1) andR^(N2) is, independently, H or optionally substituted alkyl, or R^(N1)and R^(N2), taken together with the nitrogen atom to which each areattached, form a heterocyclyl group, as defined herein.

By “thio” is meant an —S— group

By “thiol” is meant an —SH group.

By “triflate” is meant an —OSO₂—CF₃ or —OTf group.

By “triflimide” is meant an —N(SO₂—CF₃)₂ or —NTf₂ group.

By “trifyl” or “Tf” is meant an —SO₂—CF₃ group.

By “attaching,” “attachment,” or related word forms is meant anycovalent or non-covalent bonding interaction between two components.Non-covalent bonding interactions include, without limitation, hydrogenbonding, ionic interactions, halogen bonding, electrostaticinteractions, π bond interactions, hydrophobic interactions, inclusioncomplexes, clathration, van der Wails interactions, and combinationsthereof.

As used herein, the terms “top,” “bottom,” “upper,” “lower,” “above,”and “below” are used to provide a relative relationship betweenstructures. The use of these terms does not indicate or require that aparticular structure must be located at a particular location in theapparatus.

Other features and advantages of the invention will be apparent from thefollowing description and the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic of an exemplary polymer structure having one ormore functional groups including a cationic moiety and/or a halo group(R^(AF)).

FIG. 2A-2C shows schematics of exemplary polymer structures having anaryl group including a cationic moiety and/or a halo group (Ar^(AF)) oran alkyl group including a cationic moiety and/or a halo group(Ak^(AF)). Provided are structures (A) having formulas (Ia) to (Ib); (B)having formulas (Ic) and (Id); and (C) having formulas (Ie) to (If).

FIG. 3A-3B shows schematics of exemplary polymer structures having oneor more functional groups including a cationic moiety (R^(A)) orfunctional groups including a halo group (R^(F)). Provided arestructures (A) having formulas (Ig) to (Ih); and (B) having formulas(Ii) to (Ij).

FIG. 4A-4B shows schematics of exemplary polymer structures havingR^(AF1) (i.e., a substituent that includes a cationic moiety or a halogroup) and L^(A) (i.e., a linker, such as any herein). Provided arestructures (A) having formulas (I-1) to (I-2); and (B) having formulas(I-3) to (I-4).

FIG. 5A-5B shows schematics of exemplary polymer structures havingR^(A1) (i.e., a substituent that includes a cationic moiety) or R^(F1)(i.e., a substituent that includes a halo group) and L^(A) (i.e., alinker, such as any herein). Provided are structures (A) having formulas(I-5) to (I-6); and (B) having formulas (I-7) to (I-8).

FIG. 6A-6B shows schematics of exemplary polymer structures, including(A) an exemplary polymer for an anion exchange membrane and (B) anexemplary poly(arylene ether) polymer for another anion exchangemembrane.

FIG. 7A-7B shows graphs of mechanical strength testing of (A) an anionexchange membrane including the polymer in FIGS. 6A and (B) an anionexchange membrane including the polymer in FIG. 6B. In FIG. 7A, providedare data for (i) control (Br⁻ ions); (ii) treatment with 0.5M NaOH for 1hour at 80° C. (OH⁻ ions); (iii) treatment with NaOH, then 0.5M HBr for1 hour at 25° C. (Br⁻ ions); and (iv) treatment with NaOH, then HBr, andthen NaOH (OH⁻ ions). In FIG. 7B, provided are data for (i) control;(ii) treatment with 0.01M NaOH for 1 hour at room temperature; (iii)treatment with 0.5M NaOH for 30 minutes at room temperature; and (iv)treatment with 0.5M NaOH for 30 minutes at 80° C.

FIG. 8 shows an exemplary reaction scheme to provide the polymerstructure of formula (Ih). Provided is a reaction scheme for reacting aninitial polymer (III) in the presence of a reagent (e.g., R^(H′)—X) toform a reactive polymer (IVa) having three reactive handles R^(H′)appended to three pendent aryl groups. Then, reactive polymer (IVa) istreated with a further reagent (e.g., R^(H″)—X) to form a furtherreactive polymer (IVb) having three other reactive handles R^(H″)appended to three other pendent aryl groups. Finally, polymer (IVb) istreated with a reagent (e.g., R^(A)) to form a resultant polymer (Ih)having cationic moieties (R^(A)) and halo groups (R^(F), when R^(H′) ischosen to be a chemical moiety having a halo group). In thisnon-limiting manner, orthogonal chemistries can be installed on the samepolymer structure.

FIG. 9A-9C shows schematics of exemplary reaction schemes to providepolymer structures with one or more substituents including a cationicmoiety (R^(A)) or a halo group (R^(F1)). Provided is (A) an exemplaryreaction of a labeled Diels-Alder poly(phenylene) polymer (labeled“F-labeled DAPP”) in the presence of a reagent (e.g., R^(F)—X, such asR^(F1)—Ar—C(O)—X) to form a DAPP (IV-1) having three R^(F) substituentsappended on three pendent aryl groups of the DAPP (e.g., in which R^(F)is —C(O)—Ar—R^(F1)). Then, DAPP polymer (IV-1) is reacted with a secondreagent (e.g., R^(H)—X, such as R^(H1)—Ar—C(O)—X) to form hydrophobicDAPP (IV-2) having three R^(H) substituents appended on three otherpendent aryl groups of the DAPP (e.g., in which R^(H) is—C(O)—Ar—R^(H1)). Also provided is (B) a reaction to form a cationic,hydrophobic film using polymer (IV-2), which was provided as a cast filmand then reacted in the presence of a reagent (e.g., R^(A1)) to providepolymer (IV-3) including cationic moieties (e.g., R^(A) that is—C(O)—Ar—R^(A1), in which R^(A1) is an onium) and halo groups (e.g.,R^(F) that is —C(O)—Ar—R^(F1), in which R^(F1) is halo). Alternatively,the reaction includes forming a cation moiety and then casting thepolymer, as shown in (C), in which polymer (IV-2) is reacted in thepresence of a reagent (e.g., R^(A1)) to provide polymer (IV-3) includingcationic moieties (e.g., R^(A) that is —C(O)—Ar—R^(A1), in which R^(A1)is an onium) and halo groups (e.g., R^(F) that is —C(O)—Ar—R^(F1), inwhich R^(F1) is halo). Then, polymer (IV-3) is cast as film. In anyembodiment herein, the anion is R^(H1). Alternatively, an anion exchangereaction can be conducted, thereby swapping R^(H1) for any other usefulanion (e.g., any described herein).

FIG. 10 shows a schematic of an exemplary reaction scheme to providepolymer structure (IV-5). Provided is an exemplary reaction of ahydrophobic DAPP (IV-2) having three R^(H) substituents appended onthree pendent aryl groups of the DAPP (e.g., in which R^(H) is—C(O)—Ar—R^(H1)) and three R^(F) substituents appended on three otherpendent aryl groups (e.g., in which R^(F) is —C(O)—Ar—R^(F1)).Additional reaction steps can be conducted to modify the linker. In oneinstance, under reducing conditions, the carbonyl linker (—C(O)—) isreduced to a methylene linker (—CH₂—), thereby providing polymer (IV-4).This polymer is then reacted in the presence of a reagent (e.g., R^(A1))to provide polymer (IV-5) including cationic moieties R^(A) that is—CH₂—Ar—R^(A1), in which R^(A1) is an onium) and halo groups (e.g.,R^(F) that is —CH₂—Ar—R^(F1), in which R^(F1) is halo). Polymer (IV-4)can be cast as film and then reacted with a reagent R^(A1).Alternatively, polymer (IV-5) can be cast as the film.

FIG. 11 shows a schematic of an exemplary reaction scheme to providepolymer structure (IV-7). Provided is an exemplary reaction of a labeledDiels-Alder poly(phenylene) polymer (labeled “F-labeled DAPP”) in thepresence of a reagent (e.g., R^(H1)—X, such as CF₃—Ar—C(O)—Cl) to form aDAPP (IV-6) having two reactive handles R^(H1) appended to two pendentaryl groups of the DAPP (e.g., in which R^(H1) is —C(O)—Ar—CF₃); andthen a further reaction of a R^(H)-containing DAPP in the presence of areagent (e.g., R^(H1)—X, such as ClCH₂—Ar—C(O)—Cl) to form a DAPP (IV-7)having a functional group R^(H2) attached to other pendent aryl groups(e.g., in which the R^(H2) is —C(O)—Ar—CH₂Cl).

FIG. 12 shows a schematic of an exemplary reaction scheme to providepolymer structure (IV-8). Provided is an exemplary reaction of a DAPP(IV-7, provided as a cast film) with a reagent (e.g., N(CH₃)₃) toprovide polymer (IV-8) including cationic moieties (e.g., R^(A) that is—C(O)—Ar—CH₂—N(CH₃)₃, in which Ar is phenyl) and halo groups (e.g.,R^(F) that is —CH₂—Ar—CF₃, in which Ar is phenyl).

FIG. 13 shows a schematic of another exemplary reaction scheme toprovide polymer structure (IV-8). Provided is an exemplary reaction of aDAPP (IV-7) with a reagent (e.g., N(CH₃)₃) in a solvent to providepolymer (IV-8) including cationic moieties (e.g., R^(A) that is—C(O)—Ar—CH₂—N(CH₃)₃, in which Ar is phenyl) and halo groups (e.g.,R^(F) that is —CH₂—Ar—CF₃, in which Ar is phenyl). Polymer (IV-8) can becast as a film.

FIG. 14 shows a schematic of an exemplary reaction scheme to providepolymer structure (IV-10). Provided is an exemplary reaction of ahydrophobic DAPP (IV-7) having three R^(H) substituents appended onthree pendent aryl groups of the DAPP (e.g., in which R^(H) is—C(O)—Ar—CH₂Cl, in which Ar is phenyl) and three R^(F) substituentsappended on three other pendent aryl groups (e.g., in which R^(F) is—C(O)—Ar—CF₃, in which Ar is phenyl). Additional reaction steps can beconducted to modify the linker. In one instance, under reducingconditions (e.g., with HSiEt₃), the carbonyl linker (—C(O)—) is reducedto a methylene linker (—CH₂—), thereby providing polymer (IV-9). Thispolymer is then reacted in the presence of a reagent (e.g., N(CH₃)₃) toprovide polymer (IV-10) including cationic moieties e.g., R^(A) that is—CH₂—Ar—CH₂—N(CH₃)₃, in which Ar is phenyl) and halo groups (e.g., R^(F)that is —CH₂—Ar—CF₃, in which Ar is phenyl). Polymer (IV-10) can then becast as a film.

FIG. 15 shows another exemplary polymer structure (IV-11) includingcationic moieties (e.g., R^(A) that is -Ak-N(CH₃)₃, in which Ak isalkylene) and halo groups (e.g., R^(F) that is —CH₂—Ar—CF₃, in which Aris phenyl).

FIG. 16 shows an exemplary reaction scheme for reacting an initialpolymer structure having formula (V) in the presence of one or morereactive handles (R^(H)), thereby providing a polymer structure havingformula (II) in which R^(H) can be further reacted with any usefulreagent to provide any polymer herein (e.g., polymer structure havingformulas (I), (Ia) to (Ij), (I-1) to (I-8), (IV-3), (IV-5), (IV-8),(IV-10), or (IV-11), a salt thereof, or a form thereof including acounter ion). Furthermore, any of the reactive handle R^(H) in thisfigure can be reacted with a reagent to provide a R^(AF) group.

FIG. 17A-17B shows schematics of exemplary polymer structures having oneor more reactive handles (R^(H)). Provided are exemplary polymerstructures (A) having formulas (IIa) to (IId) and (B) having formulas(IIe) to (IIj). Any of the reactive handle R^(H) in this figure can bereacted with a reagent to provide a R^(AF) group.

FIG. 18A-18C shows schematics of exemplary reagents having one or morereactive end groups (R^(L)). Provided are exemplary reagent structures(A) having formulas (VI) and (VIa), (B) having formulas (VIb) and (VIc),and (C) having formula (VId).

FIG. 19A-19C shows schematics of exemplary reaction schemes to providepolymer structures with one or more reactive handles (R^(H)). Providedare (A) an exemplary reaction of a. labeled Diels-Alder poly(phenylene)polymer (labeled “F-labeled DAPP”) in the presence of a reagent (e.g.,R^(H)—X, such as R^(H1)—Ar—C(O)—X) to form a DAPP (II-1) having sixreactive handles R^(H) appended to all six pendent aryl groups of theDAPP (e.g., in which R^(H) is R^(H1)—Ar—C(O)—); (B) an exemplaryreaction of a Diels-Alder poly(phenylene) polymer (labeled “DAPP”) inthe presence of a reagent (e.g., R^(H)—X, such as R^(H1)—Ar—C(O)—X) toform a DAPP (II-2) having three reactive handles R^(H) appended to halfof the pendent aryl groups of the DAPP (e.g., in which R^(H) isR^(H1)—Ar—C(O)—); and (C) an exemplary reaction of a DAPP (II-3) havingfour reactive handles appended to four of the pendent aryl groups of theDAPP (e.g., in which R^(H) is R^(H1)—Ar—C(O)—) in the presence of anacid (e.g., H₂SO₄) to form a DAPP (II-4) having both reactive handlesand acid groups appended to the pendent aryl groups. Any of the reactivehandle R^(H) in this figure can be reacted with a reagent to provide aR^(AF) group.

FIG. 20A-20B shows schematics of further exemplary reaction schemes toprovide polymer structures with one or more reactive handles (R^(H)).Provided are (A) an exemplary reaction of a Diels-Alder poly(phenylene)polymer (labeled “DAPP”) in the presence of a reagent (e.g., R^(H)—X,such as (R^(H1))₆—Ar—C(O)—X) to form a DAPP (II-5) having three reactivehandles R^(H) appended to half of the pendent aryl groups of the DAPP(e.g., in which R^(H) is (R^(H1))₆—Ar—C(O)—); and (B) an exemplaryreaction of a Diels-Alder poly(phenylene) polymer (labeled “DAPP”) inthe presence of a reagent (e.g., R^(H)—X, such as (R^(H1))₆—Ar—SO₂—X) toform a DAPP (II-6) having three reactive handles R^(H) appended to halfof the pendent aryl groups of the DAPP (e.g., in which R^(H) is(R^(H1))₆—Ar—SO₂—). Any of the reactive moiety R^(H1) in this figure canbe reacted with a reagent to provide a R^(A1) group or a R^(F1) group.

FIG. 21A-21C shows schematics of exemplary copolymer structures having afirst segment, a linking segment, and a second segment. Provided areexemplary polymer structures (A) having formula (VII), (B) havingformula (VIII), and (C) having formula (VIIIa).

FIG. 22 shows an exemplary reaction scheme for reacting the reactivehandles (R^(H)) of an initial polymer structure having formula (II) inthe presence of one or more functional groups (R^(AF)), therebyproviding a further functionalized polymer structure having formula(IX).

FIG. 23A-23C shows schematics of exemplary polymer structures having oneor more reactive handles (R^(H)). Provided are (A) an exemplaryschematic of various portions of the DAPP that can be appended with areactive handle R^(H) (e.g., on one or more pendent groups of DAPP) orwith an acidic group (e.g., on the backbone and/or one or more pendentgroups of DAPP). Also provided are exemplary polymer structures (B)having formulas (IIk) to (IIp) and (C) having formulas (IIq) and (IIr).Any of the reactive handle R^(H) in this figure can be reacted with areagent to provide a R^(AF) group.

FIG. 24 shows schematics of exemplary polymer structures having formulas(II-7) to (II-12), which include one exemplary reactive handle R^(H) ona pendent aryl group Ar1. Any of the fluoro groups in this figure can bereacted with a reagent to provide a cationic moiety. Alternatively, thefluoro group can be maintained for use as a R^(F) group.

FIG. 25A-25C shows exemplary reaction schemes involving Diels-Alderpolyphenylene polymers (DAPPs). Provided are (A) an exemplary reactionscheme for reacting DAPP to conduct a Friedel Crafts alkyl acylationreaction, thereby producing an alkyl acylated DAPP that can be furtherreacted to provide a cationic moiety as a R^(A) group or maintained as aR^(F) group; (B) exemplary reaction schemes for reacting DAPP to conducta Friedel Crafts aryl acylation reaction; and (C) an exemplary reactionscheme showing the reaction between a silver triflate reagent (AgOTf)and a benzoyl chloride, a potential source for a reactive handle, andthen further functionalization with a phenyl group of a polymer.

FIG. 26A-26C shows reaction of a labeled DAPP in the presence of areagent to provide a reactive handle. Provided are (A) an exemplaryreaction scheme for reacting a F-labeled DAPP in the presence of areagent (e.g., R^(H)—X, such as F—Ar—C(O)—Cl) to form a DAPP (II-13)having two reactive handles R^(H) appended to two pendent aryl groups ofthe DAPP (e.g., in which R^(H) is F—Ar—C(O)—); (B) an NMR spectrographof the F-labeled DAPP; and (C) an exemplary reaction scheme for reactinga R^(H)-containing DAPP in the presence of a reagent (e.g., R^(X)—X,such as CH₃O—Ar—O—H) to form a DAPP (II-14) having a functional groupR^(X) attached to each of the two reactive handles R^(H) (e.g., in whichthe reacted R^(H) is —Ar—C(O)—, and in which R^(A) is CH₃O—Ar—O—). Anyof R^(H) and R^(X) in this figure can be reacted with a reagent toprovide a R^(AF) group, or the R^(H) can be maintained to provide aR^(F) group.

FIG. 27 shows an exemplary reaction scheme for reacting a F-labeled DAPPin the presence of a reagent (e.g., R^(H)—X, such as F—Ar—SO₂—Cl) and ametal salt (e.g., M(OTf) to form a DAPP (II-15) having nine reactivehandles R^(H) appended to six pendent aryl groups and three backbonearyl groups of the DAPP (e.g., in which R^(H) is F—Ar—SO₂—). Any of thereactive handle in this figure can be reacted with a reagent to providea R^(AF) group, or the fluoro-containing group can be maintained toprovide a R^(F) group.

FIG. 28 shows an exemplary reaction scheme for performing a Diels-Alderreaction to generate the Diels-Alder poly(phenylene) (DAPP, 3*) and forperforming a Friedel Crafts aryl acylation reaction to generate the DAPPhaving two reactive handles. Any of the reactive handle in this figurecan be reacted with a reagent to provide a R^(AF) group, or thefluoro-containing group can be maintained to provide a R^(F) group.

FIG. 29 shows further exemplary compounds having reactive handles.Provided is compound (II-17) having reactive handles (e.g., an R^(H),such as an optionally substituted aryloyl) in combination with acidicmoieties (e.g., an R^(S) group, such as —SO₃H). Also provided iscompound (II-18) having various types of reactive handles (e.g., anR^(H), such as an optionally substituted alkaryl group that issubstituted with an aminoalkyl group and/or an optionally substitutedalkaryl group that is substituted with a perfluoroalkyl group). Forcompound (II-18), each Ak is independently, an optionally substitutedalkylene group (e.g., any herein, such as an optionally substitutedmethylene, ethylene, etc.). In each of these compounds, in can be anyuseful number (e.g., any herein, such as of from about 40 to about 100).Any of the reactive handle in this figure can be reacted with a reagentto provide a R^(AF) group, or the fluoro-containing group can bemaintained to provide a R^(F) group.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to polymer structures having variousfunctional groups including a cationic moiety or a halo group (e.g., aR^(AF) group). In particular embodiments, R^(A) is a functional groupincluding the cationic moiety, and R^(F) is a functional group includingthe halo group. The R^(AF) groups can be provided on any useful site ofthe underlying polymer (e.g., pendent groups and/or backbone groups ofthe polymer). In some embodiments, the polymer includes both R^(A)groups and R^(F) groups (e.g., R^(A) and R^(F) on pendent groups and/orbackbone groups of the polymer). Described herein are structures forsuch polymers having cationic moieties or halo groups, as well asmethods for making and functionalizing such polymers.

Polymers

The present invention encompasses polymers, including copolymers.Exemplary polymer include any described herein, such as non-limitinggeneric structure provided in formulas (I), (Ia), (Ic), (Id), (Ie),(If), (Ig), (Ih), (Ii), (Ij), (VI), (VIa), (VIb), (VIc), (VId), (VII),(VIII), (VIIIa), and (IX), as well as particular structures provided asstructures (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8),(IV-3), (IV-5), (IV-8), (IV-10), and (IV-11) (see FIGS. 1, 2A-2C, 3A-3B,4A-4B, 5A-5B, 9A-9C, 10, 12-15, 18A-18C, 21A-21C, and 22), includingsalts thereof and forms thereof including a counter ion.

Of these, formulas (VI), (VIa), (VIb), (VIc), (VId), (VIII), and (VIIIa)are considered to be reagents having one or more reactive end groups.Formula (VII) is considered to be a copolymer. In particularembodiments, the copolymer of the invention includes a first segment, asecond segment, and at least one linking segment connecting at least onefirst segment with at least one second segment. The second segment canbe a hydrophilic segment or a hydrophobic segment. The first segment caninclude at least one R^(AF).

In one embodiment, a polymer includes the structure of formula (I),including salts thereof and forms thereof including a counter ion. Ascan be seen in FIG. 1, formula (I) is a generic structure encompassingother structures (e.g., formula (Ia)). The polymer can include anyuseful number of R^(AF) disposed on pendent aryl groups (e.g., arylgroups in formula (I) having an optional R³ group) and/or backbone arylgroups (e.g., aryl groups in formula (I) having an optional R¹ group orAr^(L)). The polymer can include any useful type of R^(AF) groups (e.g.,R^(A) including a cationic moiety or R^(F) including a halo group), aswell as any useful number of such groups (e.g., a groups, where a can be0, 1, 2, 3, 4, or 5, and/or where at least one a is not 0).

The polymer can include any useful type of pendent substituentssubstituents R^(AF), R^(A), R^(F), and/or R³ on a pendent aryl group,such as those labeled with an R₃ in formula (I) of FIG. 1 or withAr1—Ar6 in formula (I-3) or (I-4) of FIG. 4B), as well as any usefulnumber of such substituents on each aryl group (e.g., a substituents forR^(AF) and/or q substituents for R³, where each of a and q is,independently, 0, 1, 2, 3, 4, or 5, and/or where at least one a is not0). For any structure described herein, each R³ is, independently, afunctional group R^(AF), a functional group including a cationic moietyR^(A), a functional group including a halo R^(F), a reactive handleR^(H), an acidic moiety (e.g., R^(S), R^(P), R^(C), or any describedherein), an electron-withdrawing moiety (e.g., R^(E) or any describedherein), or an inert substituent (e.g., H, halo, optionally substitutedalkyl, optionally substituted alkoxy, etc.). In some embodiments, eachand every R³ is, independently, R^(AF), R^(A), R^(F), R^(H), R^(S),R^(P), R^(C), or R^(E). In some embodiments, fully substituted pendentgroups (e.g., R³ is not H) can provide polymers with enhanced protonconduction, enhanced anion exchange capability, and durabilitycharacteristics.

The polymer can also include any useful backbone structure. Forinstance, in formula (I), the backbone includes three groups, i.e., twoR¹-substituted aryl groups and a bridging group Ar^(L) optionallyincluding a functional group R^(AF). The polymer can include any usefultype of backbone substituents (e.g., backbone substituents R¹ or R^(H)disposed on a backbone aryl group), as well as any useful number of suchsubstituents on each group (e.g., a substituents for R^(AF) and/or qsubstituents for R¹, where each of a and q is, independently, 0, 1, 2,3, 4, or 5, and/or where at least one a is not 0). For any structuredescribed herein, each R¹ is, independently, a functional group (R^(AF),R^(A), or R^(F)), an acidic moiety (e.g., R^(S), R^(P), R^(C), or anydescribed herein), an electron-withdrawing moiety (e.g., R^(E) or anydescribed herein), or an inert substituent (e.g., H, halo, optionallysubstituted alkyl, optionally substituted alkoxy, etc.). In someembodiments, each and every R¹ is, independently, R^(AF), R^(A), R^(F),R^(H), R^(S), R^(P), R^(C), or R^(E).

Each of bridging group Ar^(L) and connecting group Ar^(M) can be anyuseful bivalent linker. In particular embodiments, each of Ar^(L) andAr^(M) is, independently, includes an optionally substituted arylenegroup. In some embodiments, each of Ar^(L) and Ar^(M) is, independently,an optionally substituted arylene group. In other embodiments, each ofAr^(L) and Ar^(M) is, independently, substituted with 1, 2, 3, or 4R^(AF) substituent(s), R^(A) substituent(s), R^(E) substituent(s), R^(H)substituent(s), R^(S) substituent(s), R^(P) substituent(s), R^(C)substituent(s), R^(E) substituent(s), or label(s). Exemplary labelsinclude a detectable label, such as an NMR label (e.g., fluorine, suchas ¹⁹F; nitrogen, e.g., ¹⁵N; or oxygen, e.g., ¹⁷O), a spin label, anisotopic label, a mass label, a fluorescent label, a dye, etc.

In yet other embodiments, each of Ar^(L) and Ar^(M) is, independently,configured to reduce meta linkages. Thus, in some instances, each ofAr^(L) and Ar^(M) is, independently, a bivalent linker formed byremoving a hydrogen atom from opposite faces of an aryl group. Examplesof such linkers include 1,4-benzenediyl (or 1,4-phenylene),2,7-phenanthrylene (or 2,7-phenanthrenediyl), 1,5-naphthylene (or1,5-napthalenediyl), etc. For example, the polymer can include astructure of Formula (I) but having Ar^(L) as a R¹-substituted1,4-phenylene and Ar^(M) as an R¹-substituted 1,4-phenylene, anR³-substituted 1,4-phenylene, an R^(AF)-substituted 1,4-phenylene, anR^(A)-substituted 1,4-phenylene, or an R^(F)-substituted 1,4-phenylene.

A polymer can include any useful number of structures of formula (I). Insome embodiments, the polymer includes in structures, where in is aninteger of from about 1 to 1000 (e.g., from about 1 to 500).

Functional groups R^(AF) can be present on the same polymer or on thesame segment of the polymer with any other different type ofsubstitutions, e.g., reactive handle substitutions (e.g., R^(H)), acidicsubstitutions (e.g., R^(S), R^(P), and/or R^(C), as well as combinationsthereof) and R^(E) substitutions. In particular embodiments, R^(A)groups can be employed to install functional groups to promote bindingto an anion, and R^(F) groups can be employed to provide hydrophobiccharacteristics. In other embodiments, the use of acidic moieties andelectron-withdrawing moieties could provide orthogonal chemistries tocontrol and optimize performance (e.g., by employing acidic moieties tocontrol ion conduction) and durability (e.g., by employingelectron-withdrawing moieties to reduce oxidation). Further, thepresence of a reactive handle R^(H) allows the polymer to be furtherfunctionalized (e.g., with one or more functional groups R^(AF), R^(A),R^(F), R^(S), R^(P), R^(C), and/or R^(E), as well as any other groupsdescribed herein). In one instance, each pendent aryl group issubstituted with an R^(AF) (e.g., an R^(A) and/or an R^(F)), an R^(H),an R^(S), an R^(P), an R^(C), and/or an R^(E). Optionally, one or morebackbone aryl groups can be further substituted with an R^(AF) (e.g., anR^(A) and/or an R^(F)), an R^(H), an R^(S), an R^(P), an R^(C), and/oran R^(E).

As seen in FIG. 2A, formulas (Ia) and (Ib) provide polymers havingdifferent representations of the R^(AF) functional group. As can beseen, formula (Ia) includes a R^(AF) moiety in which each moietyincludes a linker L^(A) and an optionally substituted aryl group Ar^(AF)including a cationic moiety or a halo. As seen in formula (Ib), theR^(AF) moiety includes a linker L^(A) and an optionally substitutedalkyl group Ak^(AF) including a cationic moiety or a halo. Linker L^(A)can include any useful linker moiety described herein, such as acovalent bond, carbonyl, oxy, thio, azo, phosphonoyl, phosphoryl,sulfonyl, sulfonyl, sulfonamide, imino, imine, phosphine, nitrilo,optionally substituted C₁₋₁₂ alkylene, optionally substituted C₁₋₁₂alkyleneoxy, optionally substituted C₁₋₁₂ heteroalkylene, optionallysubstituted C₁₋₁₂ heteroalkyleneoxy, optionally substituted C₄₋₁₈arylene, or optionally substituted C₄₋₁₈ aryleneoxy.

The aryl group Ar^(AF) can be any useful aryl group (e.g., any herein,such as phenyl, benzyl, etc.) that is optionally substituted (e.g., anygroup herein described for an aryl group) and that also includes eithera cationic moiety (e.g., any herein, such as an ammonium cation, asulfonium cation, a phosphonium cation, an oxonium cation, a diazoniumcation, or a halonium cation) and/or a halo (e.g., any herein, such asfluoro, chloro, bromo, or iodo). The alkyl group Ak^(AF) can be anyuseful alkyl group (e.g., any herein, such as methyl, propyl, butyl,etc.) that is optionally substituted (e.g., any group herein describedfor an alkyl group) and that also includes either a cationic moiety(e.g., any herein, such as an ammonium cation, a sulfonium cation, aphosphonium cation, an oxonium cation, a diazonium cation, or a haloniumcation) and/or a halo (e.g., any herein, such as fluoro, chloro, bromo,or iodo).

The R^(AF) moiety can be present on any useful sites within a polymer.As seen in FIG. 2B, formulas (Ic) and (Id) provide polymers havingR^(AF) functional groups on pendent aryl groups (i.e., a number of—L^(A)-Ar^(AF) groups on pendent aryl groups of formula (Ic) and anumber of —L^(A)-Ak^(AF) groups on pendent aryl groups of formula (Id)).As seen in FIG. 2C, different combinations of R^(AF) moieties includingaryl and alkyl groups are present on the same polymer. For instance,formula (Ie) provides a polymer having both —L^(A)-Ar^(AF) groups and—L^(A)-Ak^(AF) groups on backbone and pendent aryl groups. In anotherinstance, formula (If) provides a polymer having both —L^(A)-Ar^(AF)groups and —L^(A)-Ak^(AF) groups on pendent aryl groups.

An R^(AF) moiety can either be a functional group including a cationicmoiety (e.g., R^(A)) or a functional group including a halo (e.g.,R^(F)) and a polymer can have any useful combination of R^(A) and R^(F)groups. As seen in FIG. 3A, formula (Ig) includes a cationic R^(A) groupon three pendent aryl groups, a halo-containing R^(F) group on threeother pendent aryl groups, and an R^(AF) group on backbone aryl groups.Formula (Ih) includes a cationic R^(A) group on three pendent arylgroups, as well as a halo-containing R^(F) group on three other pendentaryl groups. As seen in FIG. 3B, formula (Ii) includes a cationic R^(A)group on four pendent aryl groups, a halo-containing R^(F) group on twopendent aryl groups, and an R^(AF) group on backbone aryl groups.Formula (Ij) includes a cationic R^(A) group on four pendent arylgroups, as well as a halo-containing R^(F) group on two pendent arylgroups.

FIG. 29 provides an exemplary polymer of formula (II-18) having afunctional group with a cationic moiety (R^(A), e.g., -Ak-Ph-Ak-NMe₃)and a functional group including a halo (R^(F), e.g., -Ak-Ph-CF₃).

Polymer Reagents

The present invention also includes reagents having any useful polymersegment described herein. For instance, the reagent can include apolymer segment disposed between two reactive end groups, where each endgroup can be the same or different. The polymer segment can be anydescribed herein (e.g., a structure provided in formula (I), (Ia), (Ib),(Ic), (Id), (Ie), (If), (Ig), (Ii), (Ij), (VI), (VIa), (VIb), (VIc),(VId), (VII), (VIII), (VIIIa), and (IX), as well as particularstructures provided as structures (I-1), (I-2), (I-3), (I-4), (I-5),(I-6), (I-7), (I-8), (IV-3), (IV-5), (IV-8), (IV-10), and (IV-11)). Inaddition, the polymer segment can include a second segment (e.g., Ar*),such as any described herein.

Optionally, a sublink L′ can be present between the polymer segment anda reactive end group. The sublink L′ can be composed of any usefullinkage, such as any described herein (e.g., those described for linkingsegment L).

The reactive end group can be any useful group configured to react witha second reactive end group. In this way, ordered copolymer blockstructures can be synthesized by selectively placing reactive end groupson the ends of blocks or segments to form polymer reagents, and thenreacting that polymer reagent to place the segments in an end-to-endfashion in the copolymer. A skilled artisan would understand how toplace reactive end groups in a polymer reagent in order to form acopolymer with the desired configuration or order.

The reactive end group is usually placed on the ends of a first polymerreagent, as well as on the ends of the second polymer reagent. Then, afirst reactive end group on the first polymer reagent reacts with thesecond reactive end group on a second polymer reagent. The first andsecond reactive end groups can be chosen from a pair of co-reactivegroups. For example, such pairs of co-reactive groups include (i) anucleophile for use with (ii) an electrophile; (i) an optionallysubstituted aryl group (e.g., having a —C(O)R^(I) group, where R^(I) isan aryl group having one or more halo) for use with (ii) an optionallysubstituted aryl group (e.g., having a —OR^(Pr) group, where R^(Pr) is Hor an O-protecting group that can be deprotected prior to conducting areaction); (i) an optionally substituted aryl group (e.g., having a—C(O)R^(I) group, where R^(I) is an aryl group having one or more halo)for use with (ii) an optionally substituted alkoxy group (e.g., such as—OR^(Pr), where R^(Pr) is H or an O-protecting group that can bedeprotected prior to conducting a reaction); (i) an optionallysubstituted aryl group for use with (ii) an optionally substitutedalkoxy group (e.g., such as —OR^(Pr), where R^(Pr) is H or anO-protecting group that can be deprotected prior to conducting areaction); (i) an optionally substituted alkynyl group for use with (ii)an optionally substituted azido group, which can participate in aHuisgen 1,3-dipolar cycloaddition reaction; as well as (i) an optionallysubstituted diene having a 4π electron system for use with (ii) anoptionally substituted dienophile or an optionally substitutedheterodienophile having a 2π electron system, which can participate in aDiels-Alder reaction. For the co-reactive groups above, reagent (i)reacts with reagent (ii) in each pair. In one instance, the reactivegroup is R^(H) (e.g., any described herein).

An exemplary polymer reagent is provided as structure (VI) in FIG. 18A.As can be seen, polymer reagent (VI) includes a two reactive end groupsR^(L) with a polymer segment (in brackets) placed between the reactiveend groups. For this exemplary reagent, the optional sublink L′ islocated between the polymer segment and one of the reactive end groups.For reagent (VI), the polymer segment is that of formula (I), but anyformula or structure herein can be employed for this polymer segment.

Further exemplary polymer reagents are provided as structure (VIa) to(VId) in FIG. 18A-18C. Exemplary reagents include a polymer havingstructure (VIa) to (VId), which includes a sublink having a structuresimilar to that of Formula (I) but lacking aryl group Ar^(M).

Copolymers

The present invention also includes copolymers. In one embodiment, thecopolymer includes the structure of formula (VII), including saltsthereof. As can be seen in FIG. 21A, formula (VII) is a genericstructure. Similar to formula (I) described above, the copolymerstructure includes R^(AF)-substituted pendent and/or backbone arylgroups, R¹-substituted aryl groups, bridging group Ar^(L), connectinggroup Ar^(M), pendent substituents R³, and m units. Thus, thedescription for these substituents provided for formula (I) appliesequally to formula (VII). In some embodiments, each of Ar^(L) and Ar^(M)is, independently, an optionally substituted phenylene. In otherembodiments, each of Ar^(L) and Ar^(M) is, independently, an optionallysubstituted 1,4-phenylene, e.g., Ar^(L) as a R¹-substituted1,4-phenylene and/or Ar^(M) as an R²-substituted 1,4-phenylene.

FIG. 21B provides formula (VIII), which is another generic structureincluding a first segment, a linking segment, a second segment, and tworeactive end groups R^(L). The first segment can be any described herein(e.g., a structure having formula (I)). The reactive end group R^(L) canbe any described herein. As seen in FIG. 21C, the structure of formula(VIIIa) includes a reactive end group R^(L) that is an optionallysubstituted aryl group (e.g., an aryl group having a number of R^(AF)groups).

Formulas (VII) and (VIII) also include additional groups, including alinking segment L and a second segment Ar* of n units. The linkingsegment L can be any useful linkage (e.g., any herein), including thoseto form a covalent bond between the two segments. In some embodiments,the linking segment includes those composed of structures, or a portionof such structures, in the first segment and/or the second segment.Exemplary linking segments L include a covalent bond, an optionallysubstituted alkylene, an optionally substituted heteroalkylene, anoptionally substituted alkyleneoxy, an optionally substitutedheteroalkyleneoxy, an optionally substituted arylene, an optionallysubstituted aryleneoxy, an Ar* unit, or a structure of formula (I).

The copolymer having formulas (VII) and (VIII) can have any usefulsecond segment Ar*. In some embodiments, Ar* includes a structure offormula (I) (e.g., where each R³ is H, optionally substituted alkyl, orR^(E); or where the number of R^(S) substituents in Ar* is less than thenumber of R^(S) and/or R^(P) substituents in the hydrophilic segment); ahydrophobic subunit; a sulfone subunit (e.g., a subunit including an—SO₂— group); an arylene sulfone subunit (e.g., —(Ar)_(a)—SO₂—(Ar)_(b)—,where Ar is an optionally substituted arylene group, as defined herein,and each a and b is an integer of about 0 to 10 and at least one of a orb is 1 or more); an ether sulfone subunit (e.g.,—(X¹)_(a)—SO₂—(X²)_(b)—O— or —X¹—O—X² SO₂—, where each X¹ and X² is,independently, any useful group, such as optionally substituted aryleneor optionally substituted alkylene, and each a and b is an integer ofabout 0 to 10 and at least one of a or b is 1 or more); an arylene ethersubunit (e.g., —(Ar)_(a)—O—(Ar)_(b)—, where Ar is an optionallysubstituted arylene group, as defined herein, and each a and b is aninteger of about 0 to 10 and at least one of a or b is 1 or more); anarylene ketone subunit (e.g., —(Ar)_(a)—C(O)—(Ar)_(b)—, where Ar is anoptionally substituted arylene group, as defined herein, and each a andb is an integer of about 0 to 10 and at least one of a or b is 1 ormore); a perfluoroalkyl subunit (e.g., —(CF₂)_(f1)—, where f1 is aninteger of 1 to about 16); or a perfluoroalkoxy subunit (e.g.,—O(CF₂)_(f1)—, —(CF₂)_(f1)O—, —O(CF₂)_(fl)CF(CF₃)O(CF₂)_(f2)—,>CFO(CF₂)_(fl)CF(CF₃)O(CF₂)_(f2)—, where each f1 and f2 is,independently, an integer of 1 to about 16).

In some embodiments, formulas (VII) and (VIII) include a second segmentAr* that is a hydrophobic segment. In some embodiments, the secondsegment Ar* is a hydrophobic segment having one or moreelectron-withdrawing moieties (e.g., R^(E)) or one or morehalo-containing functional groups (e.g., R^(F)). In particularembodiments, each pendent aryl group in the polymer or a segment thereofis substituted with an R^(E) substitution and/or an R^(F) substitution,where each substitution may be the same or different. In otherembodiments, both pendent and backbone aryl groups are each,independently, substituted with an R^(E) substitution and/or an R^(F)substitution.

In other embodiments, formulas (VII) and (VIII) include a second segmentAr* that is a hydrophilic segment. In some embodiments, the secondsegment Ar* is a hydrophilic segment that includes the twoR¹-substituted aryl groups and a bridging group Ar^(L). Thus, in someembodiments, at least one substituent in this hydrophilic segment (e.g.,substituents R¹, R², or R³) is a hydrophilic moiety (e.g., an acidicmoiety, such as any R^(A), R^(S), R^(P), and/or R^(C) described hereinor any moiety including a sulfonyl group or a phosphoryl group). In someembodiments, the hydrophilic segment includes one or more acidicmoieties (e.g., R^(S), R^(P), and/or R^(C), as well as combinationsthereof) on only the pendent aryl groups. Exemplary hydrophilic segmentsinclude those having R^(A)-substituted pendent aryl groups,R^(S)-substituted pendent aryl groups, R^(P)-substituted pendent arylgroups, and R¹-substituted backbone aryl groups.

A copolymer can include any useful number or ratio of first and secondsegments (e.g., hydrophilic and hydrophobic segments). In someembodiments, formulas (VII) and (VIII) include m number of firstsegments (e.g., hydrophilic segments) and n number of second segments(e.g., hydrophobic segments), where each of m and n is, independently,an integer of from about 1 to 1000. In other embodiments, the m (thenumber of first segments) is minimized in order to minimize swelling ofthe copolymer. For example, in some instances, m<n. In other instance, nis at least about 5 times greater than m (e.g., n is about 10 timesgreater than m, or n is about 20 times greater than m). In yet otherinstances, m is of from about 1 to 100, and n is of from about 5 to 500(e.g., m is of from about 1 to 50, and n is of from about 5 to 500; m isof from about 1 to 50, and n is of from about 10 to 100; m is of fromabout 1 to 10, and n is of from about 5 to 500; m is of from about 1 to20, and n is of from about 20 to 400; and m is of from about 1 to 10,and n is of from about 100 to 200). In some instances, m can be about5.6 and n can be about 60.7 or 121.4. In other instances, m is of fromabout 1 to 20, and n is of from about 20 to 400.

For any polymer herein, including any copolymer herein, each and everyR¹ can be independently, R^(AF), R^(A), R^(F), R^(H), R^(S), R^(P),R^(C), and/or R^(E). For instance, in some embodiments, each aryl groupin the polymer or a segment thereof is substituted with an R^(AF), anR^(A), an R^(F), an R^(H), an R^(S), an R^(P), and/or an R^(C)substitution, where each substitution may be the same or different.Reactive handles R^(H) can be present on the same polymer or on the samesegment of the polymer with any other different type of substitutions,e.g., acidic substitutions (e.g., R^(S), R^(P), and/or R^(C), as well ascombinations thereof) and R^(E) substitutions, In particular, the use ofacidic moieties and electron-withdrawing moieties could provideorthogonal chemistries to control and optimize performance (e.g., byemploying acidic moieties to control ion conduction) and durability(e.g., by employing electron-withdrawing moieties to reduce oxidation).Further, the presence of a reactive handle R^(H) allows the polymer tobe further functionalized (e.g., with one or more functional groupsR^(AF), R^(A), R^(F), R^(S), R^(P), R^(C), and/or R^(E)). In oneinstance, each pendent aryl group is substituted with an R^(AF), anR^(A), an R^(F), an R^(H), an R^(S), an R^(P), an R^(C), and/or anR^(E). Optionally, one or more backbone aryl groups can be furthersubstituted with an R^(AF), an R^(A), an R^(F), an R^(H), an R^(S), anR^(P), an R^(C), and/or an R^(E).

Functional Groups and Moieties

The present invention includes the use of functional groups andmoieties, such as functional groups (e.g., R^(AF)) including a cationicmoiety (e.g., R^(A)) or a halo (e.g., R^(F)), reactive handles (e.g.,R^(H)), acidic moieties (e.g., R^(S), R^(P), or R^(C)),electron-withdrawing moieties (e.g., R^(E)), and other functionalgroups. Any number of these functional moieties can be present on thepolymer (e.g., the polymer backbone aryl groups and/or pendent arylgroups).

Exemplary functional groups (e.g., R^(AF)) including any useful groupincluding a cationic moiety (e.g., an onium, such as any describedherein) or a halo (e.g., any described herein). In some embodiments, thefunctional group R^(AF) includes -L^(A)-Ar^(AF) or -L^(A)-Ak^(AF), inwhich Ar^(AF) is an optionally substituted aryl and in which Ak^(AF) isan optionally substituted alkyl or optionally substituted heteroalkyl.In particular embodiments L^(A) is any useful covalent bond or anyuseful linker (e.g., any described herein). In some embodiments, Ar^(AF)or Ak^(AF) is substituted with one or more substituents selected fromthe group of halo, cyano, optionally substituted haloalkyl, optionallysubstituted perfluoroalkyl, optionally substituted nitroalkyl, andoptionally substituted alkyl; and further includes a cationic moiety(e.g., an onium cation) or a halo (e.g., fluoro, or any describedherein).

In some instances, the functional group R^(AF) is a group including alinker R^(A) and a functional moiety R^(AF1), R^(A1), or R^(F1). Inparticular embodiments, R^(AF1) is a cationic moiety or a halo. In someembodiments, R^(A1) is a cationic moiety or includes a cationic moiety(e.g., an ammonium cation, a sulfonium cation, a phosphonium cation, anoxonium cation, a diazonium cation, or a halonium cation). In otherembodiments, R^(F1) is a halo or includes a halo.

In some embodiments, R^(A1) includes N⁺. In other embodiments, R^(A1) is—N⁺R^(N1)R^(N2)R^(N3) or includes —N⁺R^(N1)R^(N2)R^(N3), where each ofR^(N1), R^(N2), and R^(N3) is, independently, H, optionally substitutedalkyl, optionally substituted aryl, or optionally substituted alkaryl;or where R^(N1) and R^(N2), taken together with the nitrogen atom towhich each are attached, form a heterocycle; or where R^(N1) and R^(N2),taken together, form an optionally substituted alkylene orheteroalkylene (e.g., as described herein). In some embodiments, each ofR^(N1), R^(N2), and R^(N3) is, independently, H or optionallysubstituted C₁₋₆ alkyl.

In some embodiments, R^(AI) includes S⁺. In other embodiments, R^(A1) is—S⁺R^(S1)R^(S2) or includes —S⁺R^(S1)R^(S2), where each of R^(S1) andR^(S2) is, independently, H, optionally substituted alkyl, optionallysubstituted aryl, optionally substituted alkaryl, or optionallysubstituted alkenyl; or where R^(S1) and R^(S2), taken together with thesulky atom to which each are attached, form a heterocycle; or whereR^(S1) and R^(S2), taken together, form an optionally substitutedalkylene or heteroalkylene (e.g., as described herein). In someembodiments, each of R^(S1) and R^(S2) is, independently, H oroptionally substituted C₁₋₆ alkyl.

In some embodiments, R^(A1) includes P⁺. In other embodiments, R^(A1) is—P⁺R^(P1)R^(P2)R^(P3) or includes —P⁺R^(P1)R^(P2)R^(P3), where each ofR^(P1), R^(P2), and R^(P3) is, independently, H, optionally substitutedalkyl, optionally substituted alkenyl, optionally substituted aryl, oroptionally substituted alkaryl; or where two of R^(P1), R^(P2), andR^(P3), taken together, form an optionally substituted alkylene orheteroalkylene (e.g., as described herein). In some embodiments, each ofR^(P1), R^(P2), and R^(P3) is, independently, H or optionallysubstituted C₁₋₆ alkyl.

In some embodiments, R^(A1) includes O⁺. In other embodiments, R^(A1) is—O⁺R^(O1)R^(O2) or includes —O⁺R^(O1)R^(O2), where each of R^(O1) andR^(O2) is, independently, H, optionally substituted alkyl, optionallysubstituted alkenyl, optionally substituted aryl, or optionallysubstituted alkaryl; or where R^(O1) and R^(O2), taken together, form anoptionally substituted alkylene or heteroalkylene (e.g., as describedherein). In some embodiments, each of R^(O1) and R^(O2) is,independently, H or optionally substituted C₁₋₆ alkyl.

In some embodiments, R^(A1) is —N₂ ⁺ or includes —N₂ ⁺.

In some embodiments, R^(A1) is —X⁺ or includes —X⁺, where X is halo asdefined herein. Exemplary halonium groups include an iodonium group(e.g., —I⁺), a bromonium group (e.g., —Br⁺), a chloronium group (e.g.,—Cl⁺), or a fluoronium group (e.g., —F⁺).

In some embodiments, R^(F1) is halo or includes halo (e.g., F, Cl, Br,or I).

As seen in FIG. 4A, formulas (I-1) and (I-2) provide polymers havingdifferent representations of the R^(AF1) functional moiety. As can beseen, formula (I-4) includes a R^(AF1) moiety attached to the pendentaryl groups by way of an aryloyl group (e.g., —C(O)-Ph). As can be alsoseen, formula (I-2) includes a R^(AF1) moiety attached to the pendentaryl groups by way of a linker L^(A) and a further aryl group (e.g.,—L^(A)-Ph). The linker L^(A) can be any useful bivalent linker. TheR^(AF1) moiety can be any useful functional group including a cationicmoiety or halo (e.g., as described herein for R^(A1) or R^(F1)).

A polymer can include any useful combination of R^(AF) groups, see,e.g., FIG. 4B. As can be seen, formula (I-3) includes a R^(AF1) moietyattached to the pendent aryl groups by way of a linker L^(A) alone or alinker with an aryl group, i.e., —L^(A)-Ph. R^(AF) groups can beprovided any useful number of pendent aryl groups in any usefullocation. As can be also seen, formula (I-4) includes a R^(AF1) moietyattached alternating pendent aryl groups by way of a linker L^(A) or afurther aryl group (e.g., —L^(A)-Ph). The linker L^(A) can be any usefulbivalent linker. The R^(AF1) moiety can be any useful functional groupincluding a cationic moiety or halo (e.g., as described herein forR^(A1) or R^(F1)).

In any formula herein, the polymer includes a functional group in whichthe cationic moiety is distanced from the backbone. For instance, whenR^(AF) is —L^(A)-R^(AF1), in which L^(A) is a linker and R^(AF1) isfunctional moiety including a cationic moiety, then L^(A) is linkerlonger than three carbon atoms (e.g., an optionally substituted C₄₋₁₈alkylene). Without wishing to be limited by mechanism, under hightemperatures (e.g., greater than about 80° C.), benzyl ammonium cationscan degrade, and it has been postulated that the hydroxyl anions cannucleophilically attack the ammonium positive charge. Thus, a long alkyltether can be employed to minimize such nucleophilic reactions, whichmay be explained by the increased steric bulk of the long alkyl chainthat may wrap around the cation protecting it from nucleophilic attack.

Each R^(AF1) functional moiety can be a functional moiety including acationic moiety (R^(A1)) or a functional moiety including a halo(R^(F1)). Each of R^(A1) and R^(F1) can be located at any usefulposition of the pendent or backbone aryl groups, see, e.g., FIG. 5A. Ascan be seen, formula (I-5) includes four R^(A1) moieties attached to thependent aryl groups by way of a linked aryl group (e.g., -L^(A)-Ph) andtwo R^(F1) moieties attached to the pendent aryl groups by way ofanother linked aryl group (e.g., -L^(A)-Ph). Formula (I-6) includesthree R^(A1) moieties attached to the pendent aryl groups by way of alinked aryl group (e.g., -L^(A)-Ph) and three R^(F1) moieties attachedto the pendent aryl groups by way of another linked aryl group (e.g.,-L^(A)-Ph).

Functional moieties R^(A1) and R^(F1) can be attached to the polymer inany useful manner, see, e.g., FIG. 5B. As can be seen, formula (I-7)includes three R^(A1) moieties attached to the pendent aryl groups byway of a linker (e.g., -L^(A)) and three R^(F1) moieties attached to thependent aryl groups by way of a linked aryl group (e.g., -L^(A)-Ph).Formula (I-8) includes three R^(A1) moieties and three R^(F1) moietiesattached to alternating pendent aryl groups by way of a linker (e.g.,-L^(A)) or a linked aryl group (e.g., -L^(A)-Ph).

Polymers having reactive handles R^(H) can be further reacted to providefunctional moieties R^(AF) on any useful polymer (e.g., a polymer havingformula (I)). Exemplary reactive handles (e.g., R^(H)) include anyuseful group, such as H, optionally substituted alkyl, optionallysubstituted haloalkyl, optionally substituted perfluoroalkyl, optionallysubstituted heteroalkyl, halo, optionally substituted aryl, optionallysubstituted alkaryl, optionally substituted arylalkoxy, optionallysubstituted aryloxy, optionally substituted aryloxycarbonyl, optionallysubstituted aryloyl, optionally substituted arylcarbonylalkyl,optionally substituted arylsulfonyl, and optionally substitutedarylsulfonylalkyl. In one instance, at least one R^(H) includes anoptionally substituted aryl group (e.g., an optionally substituted arylgroup including a halo, a haloalkyl, a perfluoroalkyl, a hydroxyl, or analkoxy group).

In some embodiments, the reactive handle R^(H) includes -L^(H)-Ar^(H) or-L^(H)-Ak^(H), in which Ar^(H) is an optionally substituted aryl and inwhich Ak^(H) is an optionally substituted alkyl or optionallysubstituted heteroalkyl. In particular embodiments L^(H) is any usefulcovalent bond or any useful linker (e.g., any described herein). In someembodiments, Ar^(H) or Ak^(H) is substituted with one or moresubstituents selected from the group of halo, cyano, optionallysubstituted haloalkyl, optionally substituted perfluoroalkyl, optionallysubstituted nitroalkyl, and optionally substituted alkyl.

FIG. 23B provides exemplary polymers having a structure that includesR^(H) substituents selected from -L^(H)-Ar^(H) and -L^(H)-Ak^(H). As canbe seen, the polymer can include one or more R^(H) that is-L^(H)-Ar^(H). In some embodiments, the Ar^(H) aryl-containing R^(H)substituent is installed on each aryl group of the polymer (e.g., as ina structure having formula (IIk)). In other embodiments, the Ar^(H)aryl-containing R^(H) substituent is installed on each pendent arylgroup of the polymer (e.g., as in a structure having formula (IIm)). Inyet other embodiments, the Ar^(H) aryl-containing R^(H) substituent isinstalled on three pendent aryl groups of the polymer (e.g., as in astructure having formula (IIo)).

In some embodiments, the Ar^(H) aryl-containing R^(H) substituent is-L^(H)-Ar^(H), in which Ar^(H) is an R^(H1)-substituted phenyl group.Furthermore, any number h of such R^(H) substituents can be installed oneach aryl group. R^(H1) can be any useful substituent, such as amino,amino, azido, nitro, nitroso, halo, as well as any described for an arylgroup (e.g., substituents (1)-(47) as defined herein for aryl). As seenin FIG. 23C, in other embodiments, the Ar^(H) aryl-containing R^(H)substituent is installed on three pendent aryl groups of the polymer(e.g., as in a structure having formula (IIq)).

In other embodiments, the Ar^(H) aryl-containing R^(H) substituent is-L^(H)-Ar^(H), in which L^(H) is a sulfonyl group and in which Ar^(H) isa halo-substituted phenyl group (e.g., pentafluorophenyl,tetrafluorophenyl, trifluorophenyl, difluorophenyl, ormonofluorophenyl). As seen in FIG. 24, exemplary polymers includestructures having formula (II-7) or structures having formula (II-8).

In yet other embodiments, the Ar^(H) aryl-containing R^(H) substituentis -L^(H)-Ar^(H), in which L^(H) is a carbonyl group and in which Ar^(H)is a halo-substituted phenyl group (e.g., pentafluorophenyl,tetrafluorophenyl, trifluorophenyl, difluorophenyl, ormonofluorophenyl). As seen in FIG. 24, exemplary polymers includestructures having formula (II-9) or structures having formula (II-10).

As can also be seen in FIG. 23B, the polymer can include one or moreR^(H) that is -L^(H)-Ak^(H). In some embodiments, the Ak^(H)alkyl-containing R^(H) substituent is installed on each aryl group ofthe polymer (e.g., as in a structure having formula (III)). In otherembodiments, the Ak^(H) alkyl-containing R^(H) substituent is installedon each pendent aryl group of the polymer (e.g., as in a structurehaving formula (IIn)). In yet other embodiments, the Ak^(H)alkyl-containing R^(H) substituent is installed on three pendent arylgroups of the polymer (e.g., as in a structure having formula (IIp)).

In some embodiments, the Ak^(H) alkyl-containing R^(H) substituent is-L^(H)-Ak^(H), in which Ak^(H) is an R^(H1)-substituted C₁-alkyl group.Furthermore, any number h of such R^(H) substituents can be installed oneach aryl group, and any number h1 of —CR^(H1)R^(H1) groups can bepresent within the R^(H) substituent, in which each R^(H1) can be thesame or different. R^(H1) can be any useful substituent, such as amino,amido, azido, nitro, nitroso, halo, as well as any described for an arylgroup (e.g., substituents (1)-(27) as defined herein for alkyl). As seenin FIG. 23C, in other embodiments, the Ak^(H) alkyl-containing R^(H)substituent is installed on three pendent aryl groups of the polymer(e.g., as in a structure having formula (IIr)).

In other embodiments, the Ak^(H) alkyl-containing R^(H) substituent is-L_(H)-Ak^(H), in which L^(H) is a carbonyl group and in which Ak^(H) isa halo-substituted alkyl group (e.g., perfluoroalkyl, —(CF₂)_(h1)F,—(CH₂)_(h1)F, or —(CHF)_(h1)F, in which h1 is an integer of from about 1to about 24). As seen in FIG. 24, exemplary polymers include structureshaving formula (II-11) or structures having formula (II-12).

Exemplary linkers (e.g., for L^(A) or L^(H)) include a covalent bond,carbonyl (—C(O)—), oxy (—O—), phosphonoyl phosphoryl (—P(O)H—),phosphoryl (—P(O)<), sulfonyl (—S(O)₂—), sulfonyl (—S(O)—), sulfonamide(e.g., —SO₂—NR^(L3)— or —NR^(L3)—SO₂—, where R^(L3) is H, optionallysubstituted alkyl, optionally substituted haloalkyl, optionallysubstituted alkoxy, optionally substituted alkaryl, optionallysubstituted aryl, or halo), imino (—NH—), imine (e.g., —CR^(L1)═N—,where R^(L1) is H or optionally substituted alkyl), phosphine (e.g.,—PR^(L3)— group, where R^(L3) is H or optionally substituted alkyl),nitrilo (e.g., —NR^(L3)—, where R^(L3) is H, optionally substitutedalkyl, optionally substituted haloalkyl, optionally substituted alkoxy,optionally substituted alkaryl, optionally substituted aryl, or halo),optionally substituted C₁₋₁₂ alkylene (e.g., —(CR^(L1)R^(L2))_(La)-,where each of R^(L1) and R^(L2) is, independently, H, optionallysubstituted alkyl, optionally substituted haloalkyl, optionallysubstituted alkoxy, optionally substituted alkaryl, optionallysubstituted aryl, or halo), optionally substituted C₁₋₁₂ alkyleneoxy,optionally substituted C₁₋₁₂ heteroalkylene (e.g., —C(O)NR^(L3)—,—NR^(L3)C(O)—, —(CR^(L1)R^(L2))_(La)—C(O)—NR^(L3)—,—(CR^(L1)R^(L2))_(La)—NR^(L3)—C(O)—, —(CR^(L1)R^(L2))_(La)—SO₂—NR^(L3)—,or —SO₂—NR^(L3)—(CR^(L1)R^(L2))_(La)—, where each of R^(L1), R^(L2), andR^(L3) is, independently, H, optionally substituted alkyl, optionallysubstituted haloalkyl, optionally substituted alkoxy, optionallysubstituted alkaryl, optionally substituted aryl, or halo), optionallysubstituted C₁₋₁₂ heteroalkyleneoxy, optionally substituted C₄₋₁₈arylene, or optionally substituted C₄₋₁₈ aryleneoxy.

Further exemplary reactive handles R^(H) include —C(O)—Ar^(H), in whichAr^(H) is an optionally substituted aryl (e.g., optionally substitutedphenyl with one or more optional substituents selected from the group ofhalo, haloalkyl, nitro, nitroso, alkoxy, etc.). In another instance,R^(H) includes —C(O)-Ph, in which Ph is substituted with h1 number ofR^(H1), where R^(H1) is selected from the group of halo, haloalkyl,nitro, nitroso, alkoxy, etc., and where h1 is an integer of from 1 to5).

FIG. 19A shows an exemplary reactive handle R^(H), in which R^(H1) islocated in the para position in relation to the —C(O)— linker of R^(H).As can be seen, any number of aryl groups in the underlying DAPP can besubstituted. For instance, in the polymer of structure (II-1), eachpendent aryl group (i.e., aryl groups Ar1 to Ar6) includes a R^(H)substituent of —C(O)—(p-R^(H1))-Ph. In another instance, only thebackbone aryl groups (i.e., aryl groups Ar7 to Ar9) are substituted(e.g., with one or more R^(H), such as any herein). In yet anotherinstance, the connecting group Ar^(M) (labeled aryl group Ar10) issubstituted (e.g., with one or more R^(H), such as any herein).Optionally, the connecting group Ar^(M) can include a label (e.g.,halo).

Any useful number of aryl groups in the polymer can include R^(H). Forinstance, as seen in FIG. 19B, the polymer of structure (II-2) includesthree pendent aryl groups, in which each of these pendent groupsincludes a R^(H) substituent of —C(O)—(p-R^(H1))-Ph. In some instances,each pendent aryl group is substituted. In other instances, only some ofthe pendent groups are substituted.

The polymer structure can include any useful combination ofsubstitutions, including one or more R^(H) substituents in combinationwith one or more R¹ and/or R³ substituents. For instance, as seen inFIG. 19C, the polymer of structure (II-4) includes four R^(H)substituents (e.g., —C(O)—(p-R^(H1))-Ph located on pendent aryl groups),a R¹ substituent (e.g., —SO₃H located on a backbone aryl group), and twoR³ substituents (e.g., —SO₃H located on pendent aryl groups). Any usefulnumber and type of R^(H), R¹, and/or R³ substituents can be present on aparticular polymer structure. In another instance, the number q of R¹substituent(s) is of from 0 to 5 for each aryl group (e.g., from 0 to 1,1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, or 2 to 3).

In one instance, the number h of R^(H) substituent(s) is of from 0 to 5for each aryl group (e.g., from 0 to 4, 0 to 3, 0 to 2, 0 to 1, 1 to 5,1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, or 2 to 3). In some embodiments,each aryl group includes one or more R^(H). In other embodiments, onearyl group includes one or more R^(H). In other embodiments, eachpendent aryl group includes one or more R^(H). In yet other embodiments,one to three pendent aryl groups includes one or more R^(H). In otherembodiments, each backbone aryl group or Ar^(L) aryl group includes oneor more R^(H). In some embodiments, one backbone aryl group includes oneor more R^(H). In particular embodiments, each h for each aryl group isthe same or different.

In another instance, each backbone aryl group or Ar^(L) aryl groupincludes one or more R¹. In particular embodiments, each q for each arylgroup is the same or different. In yet another instance, the number q ofR³ substituent(s) is of from 0 to 5 for each aryl group (e.g., from 0 to1, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, or 2 to 3). in someembodiments, each pendent aryl group includes one or more R³.

Any useful R^(H) substituents can be present on any number of arylgroups (e.g., some of the pendent aryl groups, such as of from about 1to about 3 pendent aryl groups). For instance, FIG. 20A provides anotherpolymer of structure (II-5), which includes three pendent aryl groups(i.e., pendent aryl groups Ar1, Ar4, and Ar6) and in which each of thesependent groups includes a R^(H) substituent of —C(O)—(R^(H1))5-Ph. Inanother instance, FIG. 20B provides another polymer of structure (II-6),which includes three pendent aryl groups (i.e., pendent aryl groups Ar1,Ar4, and Ar6) and in which each of these pendent groups includes a R^(H)substituent of 13 SO₂—(R^(H1))5-Ph.

Other exemplary reactive handles R^(H) include —SO₂—Ar^(H), in whichAr^(H) is an optionally substituted aryl (e.g., optionally substitutedphenyl with one or more optional substituents selected from the group ofhalo, haloalkyl, nitro, nitroso, alkoxy, etc.). In another instance,R^(H) includes —SO₂-Ph, in which Ph is substituted with h1 number ofR^(H1), where R^(H1) is selected from the group of halo, haloalkyl,nitro, nitroso, alkoxy, etc., and where h1 is an integer of from 1 to5).

Exemplary acidic moieties (e.g., R^(S)) include any group having one ormore sulfonyl groups, such as sulfo (e.g., —SO₂—OH), alkylsulfonyl(e.g., —SO₂—R^(S1), where R^(S1) is optionally substituted C₁₋₁₂ alkyl),alkylsulfonylalkyl (e.g., —R^(SA)—SO₂—R^(S1), where each of R^(S1) isoptionally substituted C₁₋₁₂ alkylene or optionally substitutedheteroalkylene and R^(S1) is optionally substituted C₁₋₁₂ alkyl),arylsulfonyl (e.g., —SO₂—R^(Ar), where R^(Ar) is optionally substitutedC₄₋₁₈ aryl), arylsulfonylalkyl (e.g., —R^(SA)—SO₂—R^(Ar), where R^(SA)is independently, optionally substituted C₁₋₁₂ alkyl or alkylene andR^(Ar) is optionally substituted C₄₋₁₈ aryl), sulfonamoyl (e.g.,—SO₂NR^(N1)R^(N2)), sulfoamino (e.g., —N(R^(N1))—SO₂—R^(S3)),aminosulfonyl (e.g., —SO₂—NR^(N1)—R^(S2)), or sulfonyl imide (e.g.,—SO₂—NR^(N1)—SO₂—R^(S3)), where each of R^(N1) and R^(N2) is,independently, H, optionally substituted C₁₋₁₂ alkyl (e.g., haloalkyl,such as perfluoroalkyl), optionally substituted C₄₋₁₈ aryl, oroptionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl; R^(S2) is H, optionallysubstituted C₁₋₁₂ alkyl (e.g., haloalkyl, such as perfluoroalkyl),hydroxyl, optionally substituted C₁₋₁₂ alkylsulfonyl, optionallysubstituted C₄₋₁₈ aryl, or optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl;and R^(S3) is H, hydroxyl, optionally substituted C₁₋₁₂ alkyl (e.g.,haloalkyl, such as perfluoroalkyl), optionally substituted C₄₋₁₈ aryl,or optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl.

In any of these moieties, each R^(S1) and R^(S3) is, independently,optionally substituted C₁₋₁₂ alkyl (e.g., haloalkyl, such as C₁₋₁₂perfluoroalkyl), optionally substituted C₁₋₁₂ alkoxy, optionallysubstituted C₄₋₁₈ aryl, optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryloptionally substituted C₄₋₁₈ aryloxy, hydroxyl, or H; each R^(S2) isindependently, optionally substituted C₁₋₁₂ alkyl (e.g., haloalkyl, suchas perfluoroalkyl), optionally substituted C₁₋₁₂ alkylsulfonyl,optionally substituted C₁₋₁₂ alkoxy, optionally substituted C₄₋₁₈ aryl,optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl optionally substituted C₄₋₁₈aryloxy, hydroxyl, or H; each R^(Ar) is, independently, optionallysubstituted C₄₋₁₈ aryl, optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl, oroptionally substituted C₄₋₁₈ aryloxy; each of R^(SA) is, independently,oxy, optionally substituted C₁₋₁₂ alkylene, or optionally substitutedheteroalkylene; and each of R^(N1) and R^(N2) is, independently, H,optionally substituted C₁₋₁₂ alkyl (e.g., haloalkyl, such asperfluoroalkyl), optionally substituted C₄₋₁₈ aryl, or optionallysubstituted C₁₋₁₂ alk-C₄₋₁₈ aryl.

Other exemplary acidic moieties (e.g., R^(P)) include any group havingone or more phosphoryl groups, such as phosphono (e.g., —P(O)(OH)₂),phosphoric ester (e.g., —O—PO(OH)₂ or —O—P(O)<R^(P1)R^(P2) or—O—P(O)<R^(Ar)R^(P2) or —O—P(O)<R^(Ar)R^(Ar), where each R^(Ar) is thesame or different), alkylphosphoryl (e.g., —P(O)<R^(P1)R^(P2), whereR^(P1) is optionally substituted C₁₋₁₂ alkyl or optionally substitutedC₁₋₁₂ alkoxy; and R^(P2) is optionally substituted C₁₋₁₂ alkyl,optionally substituted C₁₋₁₂ alkoxy, optionally substituted C₄₋₁₈ aryl,optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl, optionally substitutedC₄₋₁₈ aryloxy, hydroxyl, or H), substituted phosphonoyl (e.g.,—P(O)HR^(P1), where R^(P1) is optionally substituted C₁₋₁₂ alkyl,optionally substituted C₁₋₁₂ alkoxy, optionally substituted C₄₋₁₈ aryl,optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl, optionally substitutedC₄₋₁₈ aryloxy, hydroxyl, or H), alkylphosphorylalkyl (e.g.,—R^(PA)—P(O)<R^(P1)R^(P2), where R^(PA) is optionally substituted C₁₋₁₂alkylene or optionally substituted heteroalkylene; and each of R^(P1)and R^(P2) is, independently, optionally substituted C₁₋₁₂ alkyl,optionally substituted C₁₋₁₂ alkoxy, optionally substituted C₄₋₁₈ aryl,optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl, optionally substitutedC₄₋₁₈ aryloxy, hydroxyl, or H), arylphosphoryl (e.g., —P(O)<R^(Ar)R^(P2)or —P(O)<R^(Ar)R^(Ar), where each R^(Ar) is, independently, optionallysubstituted C₄₋₁₈ aryl, optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl, oroptionally substituted C₄₋₁₈ aryloxy; and R^(P2) is optionallysubstituted C₁₋₁₂ alkyl, optionally substituted C₁₋₁₂ alkoxy, optionallysubstituted C₄₋₁₈ aryl, optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl,optionally substituted C₄₋₁₈ aryloxy, hydroxyl, or H), orarylphosphorylalkyl (e.g., —R^(PA)—P(O)<R^(Ar)R^(P2) or—R^(PA)—P(O)<R^(Ar)R^(Ar), where R^(PA) is, independently, optionallysubstituted C₁₋₁₂ alkylene or optionally substituted heteroalkylene;each R^(Ar) is, independently, optionally substituted C₄₋₁₈ aryl,optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl, or optionally substitutedC₄₋₁₈ aryloxy; and R^(P2) is optionally substituted C₁₋₁₂ alkyl,optionally substituted C₁₋₁₂ alkoxy, optionally substituted C₄₋₁₈ aryl,optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl, optionally substitutedC₄₋₁₈ aryloxy, hydroxyl, or H), where each of these groups can beoptionally substituted (e.g., with one or more substituents describedfor alkyl, as defined herein).

In any of these moieties, each of R^(P1) and R^(P2) is, independently,optionally substituted C₁₋₁₂ alkyl (e.g., haloalkyl, such as C₁₋₁₂perfluoroalkyl), optionally substituted C₁₋₁₂ alkoxy, optionallysubstituted C₄₋₁₈ aryl, optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl,optionally substituted C₄₋₁₈ aryloxy, hydroxyl, or H; each of R^(Ar) is,independently, optionally substituted C₄₋₁₈ aryl, optionally substitutedC₁₋₁₂ alk-C₄₋₁₈ aryl, or optionally substituted C₄₋₁₈ aryloxy; and eachR^(PA) is, independently, oxy, optionally substituted C₁₋₁₂ alkylene, oroptionally substituted heteroalkylene.

Yet other exemplary acidic moieties (e.g., R^(C)) include any grouphaving a carbonyl group, such as carboxyl (e.g., —CO₂H), —C(O)—R^(C1),or —R^(CA)—C(O)—R^(C1) (e.g., where each R^(C1) is, independently,optionally substituted C₁₋₁₂ alkyl (e.g., haloalkyl, such as C₁₋₁₂perfluoroalkyl), optionally substituted C₁₋₁₂ alkoxy, optionallysubstituted C₄₋₁₈ aryl, optionally substituted C₁₋₁₂ alk-C₄₋₁₈ aryl,optionally substituted C₄₋₁₈ aryloxy, hydroxyl, or H; and each R^(CA)is, independently, oxy, optionally substituted C₁₋₁₂ alkylene, oroptionally substituted heteroalkylene).

Exemplary electron-withdrawing moieties (e.g., R^(E)) include optionallysubstituted C₇₋₁₁ aryloyl, optionally substituted C₆₋₁₈ aryl,carboxyaldehyde, optionally substituted C₂₋₇ alkanoyl, optionallysubstituted C₁₋₁₂ alkyl, optionally substituted C₁₋₁₂ haloalkyl,optionally substituted C₂₋₇ alkoxycarbonyl, nitro, nitroso, cyano, sulfacarboxyl, and quaternary ammonium (e.g., —N⁺R^(N1)R^(N2)R^(N3), whereeach of R^(N1), R^(N2), and R^(N3) is, independently, optionallysubstituted alkyl, optionally substituted alkaryl, or optionallysubstituted aryl, or two of R^(N1), R^(N2), and R^(N3), taken togetherwith the nitrogen atom to which each are attached, form a heterocyclylgroup, as defined herein). In another embodiment, R^(E) includes or issubstituted by a C₁₋₁₂ perfluoroalkyl group. In yet another embodiment,R^(E) is a C₁₋₁₂ perfluoroalkyl group.

One or more functional groups can be appended to a reactive handleR^(H). Exemplary functional groups include any useful group, such ashalo, nitro, nitroso, cyano, amino, amido, optionally substituted C₁₋₁₂alkyl, optionally substituted C₁₋₁₂ haloalkyl, optionally substitutedC₁₋₁₂ perfluoroalkyl, optionally substituted C₁₋₁₂ heteroalkyl,optionally substituted C₁₋₁₂ alkoxy, optionally substituted aryl,optionally substituted alkaryl, optionally substituted arylalkoxy,optionally substituted aryloxy, optionally substituted aryloxycarbonyl,optionally substituted aryloyl, optionally substituted arylsulfonyl, andoptionally substituted arylsulfonylalkyl, in addition to any thatprovides an R^(AF) (e.g., as defined herein). FIG. 22 provides astructure having the formula (IX) having h* number of R^(H)*substituents, in which R^(H)* includes a number a of reacted reactivehandle R^(H′) (e.g., a reactive handle R^(H), such as any herein,lacking a leaving group (e.g., H, halo, etc.)) that is covalently bondedto a functional group R^(AF) and includes a number h−a of non-reactedreactive handle R^(H), and in which a≤h. Any number of R^(H)substituents can include a functional group R^(AF). In one instance,every R^(H) is reacted with one or more R^(AF), thereby providing a h*number of R^(H)* and in which h* is h). In another instance, some R^(H)is reacted with one or more R^(AF), thereby providing a h* number ofR^(H)* and in which h*=a<h.

The functional moieties including a cationic moiety, functional moietiesincluding a halo, reactive handles, acidic moieties,electron-withdrawing moieties, and/or functional groups can besubstituted or unsubstituted. For example, these groups can besubstituted with one or more substitution groups, as described hereinfor alkyl and/or aryl.

Aryl groups

The aryl groups herein can have any useful configuration, structure, andsubstitutions. Exemplary aryl groups (e.g., including arylene groups,such as for Ar^(L), Ar^(M), and Ar*) include the following groups, whichmay be optionally substituted:

where each of Z, Z¹, Z², and Z³ is, independently, —O—, —S—, —SO₂—,optionally substituted alkylene, optionally substituted C₁₋₁₂alkyleneoxy, optionally substituted C₁₋₁₂ heteroalkylene, optionallysubstituted C₁₋₁₂ heteroalkyleneoxy, —CF₂—, —CH₂—, —OCF₂—,perfluoroalkylene, perfluoroalkyleneoxy, —Si(R^(i))₂—, —P(O)(R^(i))—,—PR^(i)—, —C(O)—, —C(CF₃)₂, —C(CH₃)₂—, or —CCF₃Ph-, and where R^(i) isH, optionally substituted alkyl, or optionally substituted a methyl,ethyl, isopropyl, t-butyl, or phenyl).

Polymer Salts and Forms Thereof Including a Counter Ion

The present invention includes a salt or a form thereof including acounter ion of any polymer described herein, e.g., a salt or a formthereof including a counter ion of any one of formulas (I), (Ia), (Ib),(Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (VI), (VIa), (VIb),(VIc), (VId), (VII), (VIII), (VIIIa), and (IX), as well as particularstructures provided as structures (I-1), (I-2), (I-3), (I-4), (I-5),(I-6), (I-7), (I-8), (IV-3), (IV-5), (IV-8), (IV-10), and (IV-11). Inparticular embodiments, the salt is a sodium salt. In other embodiments,the counter ion is an anion (e.g., a chloride anion or a hydroxideanion).

Polymeric Starting Material

Polymers having formula (II) can be employed as a starting material, inwhich reactive handles R^(H) can be further reacted to providefunctional moieties R^(AF) on polymer having formula (I). As can be seenin FIG. 16, formula (II) is a generic structure encompassing otherstructures (e.g., formula (IIa)), in which a polymer of formula (II) canbe optionally synthesized from an initial polymer of formula (V). Thepolymer can include any useful number of reactive handles R^(H) disposedon pendent aryl groups and/or backbone aryl groups. The polymer caninclude any useful type of reactive handles (e.g., reactive handlesR^(H)), as well as any useful number of such handles (e.g., h handles,where h can be 0, 1, 2, 3, 4, or 5, and/or where at least one h is not0).

The polymer (e.g., of formula (II) or (V)) can include any useful typeof pendent substituents (e.g., pendent substituents R^(H) and/or R³),any useful number of such substituents on each aryl group (e.g., hsubstituents for R^(H) and/or q substituents for R³, where each of h andq is, independently, 0, 1, 2, 3, 4, or 5, and/or where at least one h isnot 0), any useful backbone structure (e.g., two R¹-substituted arylgroups and a bridging group Ar^(L) optionally including a reactivehandle R^(H)), any useful type of backbone substituents (e.g., backbonesubstituents R¹ or R^(H) disposed on a backbone aryl group), and anyuseful number of such substituents on each group (e.g., h substituentsfor R^(H) and/or q substituents for R¹, where each of h and q is,independently, 0, 1, 2, 3, 4, or 5, and/or where at least one h is not0). Each of bridging group Ar^(L) and connecting group Ar^(M)can be anyuseful bivalent linker (e.g., any described herein). In particularembodiments, each of Ar^(L) and Ar^(M) is, independently, includes anoptionally substituted arylene group. Furthermore, a polymer can includeany useful number of structures of formula (I). In some embodiments, thepolymer includes In structures, where m is an integer of from about 1 to1000 (e.g., from about 1 to 500).

For any structure described herein, each R¹ or R³ is, independently, areactive handle R^(H), an acidic moiety (e.g., R^(S), R^(P), R^(C), orany described herein), an electron-withdrawing moiety (e.g., R^(F) orany described herein), or an inert substituent (e.g., H, halo,optionally substituted alkyl, optionally substituted alkoxy, etc.). Insome embodiments, each and every R¹ is, independently, R^(H), R^(S),R^(P), R^(C), or R^(E). In other embodiments, each and every R³ is,independently, R^(H), R^(S), R^(P), R^(C), or R^(E).

As seen in FIG. 17A, formulas (IIa) to (IId) provide polymers havingvarious combinations of structures for the bridging group Ar^(L) and theconnecting group Ar^(M). For example, formula (IIa) includes aconnecting group Ar^(M); formula (IIb) includes a connecting group thatis a R²-substituted 1,4-phenylene group; formula (IIc) includes aconnecting group that is a R²-substituted, R^(H)-substituted1,4-phenylene group; and formula (IId) includes a bridging group that isa R¹-substituted 1,4-phenylene group and a connecting group that is aR²-substituted, R^(H)-substituted 1,4-phenylene group. R² can be anysubstituent described herein. In some embodiments, each R² is,independently, H, halo, optionally substituted C₁₋₁₂ alkyl, optionallysubstituted C₁₋₁₂ haloalkyl, optionally substituted C₁₋₁₂perfluoroalkyl, optionally substituted C₁₋₁₂ heteroalkyl, R^(AF) (e.g.,R^(A) or R^(F)), R^(S), R^(P), R^(C), or R^(E).

As seen in FIG. 17B, formulas (IIe) to (IIj) provide polymers havingvarious R³ and R^(H) substituents on pendent aryl groups, as well asvarious R¹ and R^(H) substituents on backbone aryl groups. For instance,formula (IIe) provides a polymer having both R³ and R^(H) substituentson some of the pendent aryl groups, whereas formula (IIf) provides apolymer having either R³ or R^(H) substituents on the pendent arylgroups. In other instances, formulas (IIg) to (IIj) provide polymershaving various levels of R^(H) substitution. As can be seen, formulas(IIg) and (IIh) include R^(H) substituents on three of the pendent arylgroups. In another instance, formula (IIi) includes R^(H) substituentson all pendent and backbone aryl groups, whereas formula (IIj) includesR^(H) substituents on all pendent aryl groups.

Any polymer including an R^(H) functional moiety can be employed as astarting material (e.g., any described herein, such as in FIGS. 16,17A-17B, 19A-19C, 20A-20B, 22, 23A-23C, 24, 25A-25C, 26A-26C, 27, 28,and 29) to provide a polymer of formula (I). For instance, R^(H) can bereacted with a functional agent to provide a functional moiety includinga cationic moiety (e.g., an R^(A) group). Alternatively, an R^(H) group,if it includes a halo, can serve as a functional moiety including a halo(e.g., an R^(F) group).

Methods of Making Polymer Structures

The polymers of the invention can be synthesized using any usefulscheme. The following synthetic schemes are provided as non-limitingexamples.

FIG. 8 shows an exemplary scheme in which a polymer including reactivehandles R^(H) is further reacted to provide a polymer includingfunctional moieties having cationic moieties R^(A). As can be seen, aninitial polymer (III) is reacted in the presence of a reagent (e.g.,R^(H)′—X) to form a reactive polymer (IVa) having three reactive handlesR^(H′) appended to three pendent aryl groups. Then, reactive polymer(IVa) is treated with a further reagent (e.g., R^(H″)—X) to form afurther reactive polymer (IVb) having three other reactive handlesR^(H″) appended to three other pendent aryl groups. Finally, polymer(IVb) is treated with a reagent (e.g., R^(A)) to form a resultantpolymer (Ih) having cationic moieties (R^(A)) and halo groups whenR^(F), when R^(H′) is chosen to be a chemical moiety having a halogroup). In this non-limiting manner, orthogonal chemistries can beinstalled on the same polymer structure.

In FIG. 8, the steps to install groups R^(H′) and R^(H″) can be combinedinto a single step or can be combined into a one-pot reaction in anyuseful order (e.g., in which reagent R^(H″)—X is first introduced, andthen reagent R^(H′)—X is provided). Such groups can be selected toensure that R^(H″) displays increased reactivity to reagent R^(A), ascompared to R^(H′).

FIG. 9A-9C shows exemplary schemes for providing a functional moietyR^(F1) on a poly(phenylene)-based polymer. FIG. 9A shows an exemplaryreaction of a labeled Diels-Alder poly(phenylene) polymer in thepresence of a reagent (e.g., R^(F)—X, such as R^(F1)—Ar—C—(O)—X) to forma DAPP (IV-1) having three R^(F) substituents appended on three pendentaryl groups of the DAPP (e.g., in which R^(F) is —C(O)—Ar—R^(F1)). Then,DAPP polymer (IV-1) is reacted with a second reagent (e.g., R^(H)—X,such as R^(H1)—Ar—C(O)—X) to form hydrophobic DAPP (IV-2) having threeR^(H) substituents appended on three other pendent aryl groups of theDAPP (e.g., in which R^(H) is —C(O)—Ar—R^(H1)).

A functionalized polymer can be further reacted in any useful manner toprovide a cationic, hydrophobic polymer (e.g., as a film). For instance,FIG. 9B shows hydrophobic polymer (IV-2), which was provided as a castfilm and then reacted in the presence of a reagent (e.g., R^(A1)) toprovide polymer (IV-3) including cationic moieties (e.g., R^(A) orR^(A1)) and halo groups (e.g., R^(F) or R^(F1)). Alternatively, FIG. 9Cshows a polymer in which a cation moiety is formed and then theresultant polymer is then cast. As can be seen, polymer (IV-2) isreacted in the presence of a reagent (e.g., R^(A1)) to provide polymer(IV-3) including cationic moieties (e.g., R^(A) or R^(A1)) and halogroups (e.g., R^(F) or R^(F1)). Then, polymer (IV-3) is cast as film.Furthermore, an anion exchange reaction can be conducted, therebyswapping R^(H1) for any other useful anion (e.g., any described herein).

A functional group present on a polymer can be further reacted in anyuseful manner. In one instance, the linker includes an oxo group, whichcan be reduced with any useful reducing agent. As seen in FIG. 10, apolymer (IV-2) can include a carbonyl group, which can be reduced to amethylene group to provide polymer (IV-4). Furthermore, the polymer canbe provided as a cast film and then reacted with an amine (reagentR^(A)) to provide a polymer (IV-5) including a plurality of cationicmoieties.

As shown in Scheme I, the polymer of formula (IXa) can be formed byreacting a polymer of formula (IIi) having reactive handles, in whichpolymer (IIi) in turn can be formed by performing a Diels-Alder reactionto form the pendent and backbone aryl groups, and then performing afirst substitution reaction to introduce R^(H) to the parent structure.These steps are described in more detail below.

First, a Diels-Alder reaction can be performed with an optionallysubstituted diene, such as a1,4-bis-(2,4,5-triphenylcyclopentadienone)arylene reagent (1), with anoptionally substituted dienophile, such as a diethynylarylene reagent(2). This reaction provides a Diels-Alder poly(phenylene) polymer (DAPP)(3). As can be seen, in this step, the number of subunits m iscontrolled by the stoichiometry of reagents (1) and (2).

Second, a substitution reaction is performed with reagent R^(H)—X withthe DAPP product (3) to provide a substituted polymer (IIi), where X isany useful leaving group (e.g., halo, hydroxyl, or sulfonate, such asmesylate, tosylate, or triflate) and R^(H) is any described herein(e.g., R^(H) can be -L^(H)-Ar^(H) or —L^(H)-Ak^(H)).

The concentration of R^(H)—X can be controlled to provide the desiredextent of substitution on the DAPP pendent and/or backbone aryl groups.As can be seen, the number of R^(H) substituents h on each aryl groupcan be controlled by the stoichiometry of reagent R^(H)—X and (DAPP)(3). In one instance, concentration can be controlled in order toinstall R^(H) substituents on readily accessible pendent aryl groups.The reaction can be conducted until completion in order to access thebackbone aryl groups, which are sterically more difficult tofunctionalize.

Optionally, the substitution reaction with reagent R^(H)—X is performedin the presence of a metal salt and/or in the presence of an acid.Exemplary metal salts include M[O(SO₂—R^(MF))], M[N(SO₂—R^(MF))₂], orM[C(SO₂—R^(MF))₃], where R^(MF) is optionally substituted alkyl,optionally substituted aryl, optionally substituted alkaryl, optionallysubstituted haloalkyl, or perfluoroalkyl, and where M is Ag, Al, Ba, Bi,Ca, Cu, In, Re, Sc, Sn, Ti, Y, Yb, or Zn. Particular embodiments ofmetal salts include M[OTf]_(mf), where mf is an integer from 1 to 3 andwhere M is Ag, Al, Ba, Bi, Ca, Cu, In, Sc, Y, or Yb; as well asM[NTf₂]_(mf), where mf is an integer from 1 to 3 and where M is Ag, Al,Sn, Ti, Yb, or Zn.

Exemplary acids include a Lewis acid or a Bronsted acid that acts as acatalyst, such as, e.g., HO(SO₂—R^(AF)), HO(SO₂—R^(Ar)), HO(SO₂F),HO(SO₂—R^(Ar)), and HO(C(O)—R^(AF)), where R^(AF) is optionallysubstituted alkyl, optionally substituted aryl, optionally substitutedalkaryl, optionally substituted haloalkyl, or perfluoroalkyl, and whereR^(Ar) is optionally substituted aryl or optionally substituted alkaryl.Particular embodiments of acids include HO(SO₂CF₃), HO(SO₂F), H₂SO₄,HO(SO₂—(p-CH₃)Ph), or HO(COCF₃).

Third, a substitution reaction is performed to react a reactive handleR^(H) in the presence of a functional agent R^(AF*)—X, thereby providinga functional group R^(AF). As seen in formula (IXa), R^(AF) is formed bya reacted R^(H) group (indicated by R^(H*)) that is appended by areacted functional moiety R^(AF*). In one non-limiting example, thereactive group R^(H) can be a -Ph-CH₂Cl group that is reacted with anamine NR^(N1)—R^(N2)R^(N3) (e.g., where each of R^(N1) and R^(N2) andR^(N3) is, independently, H or optionally substituted alkyl, or R^(N1)and R^(N2), taken together with the nitrogen atom to which each areattached, form a heterocyclyl group, as defined herein), therebyproviding an R^(AF) moiety of -Ph-CH₂—NR^(N1)R^(N2)R^(N3), in whichreacted R^(H*) is -Ph-CH₂— and reacted R^(AF*) is —NR^(N1)R^(N2)R^(N3).

As shown in Scheme II, the polymer of formula (II) can be formed byperforming a Diels-Alder reaction to form the pendent and backbone arylgroups, performing a first substitution reaction to introduce R³ to theparent structure, performing a second substitution reaction to introduceR¹, and performing a final substitution reaction to introduce R^(H).Polymer (II), in turn, can be reacted (e.g., by way of a substitution orreplacement reaction) with a functional agent to provide a polymer offormula (I). The four steps to provide formula (II) are described inmore detail below.

Similar to Scheme I, the first step in Scheme II includes a Diels-Alderreaction that is performed with an optionally substituted diene, such asa 1,4-bis-(2,4,5-triphenyl cyclopentadienone)arylene reagent (1), in thepresence of an optionally substituted dienophile, such as adiethynylarylene reagent (2). This reaction provides a Diels-Alderpoly(phenylene) polymer (DAPP) (3).

The second step includes an initial substitution reaction, which isperformed with reagent R³—X in the presence of the DAPP product (3),thereby providing a substituted polymer (4). For reagent R³—X, X is anyuseful leaving group (e.g., halo, hydroxyl, or sulfonate, such asmesylate, tosylate, or triflate) and R³ is any described herein.

The third step includes a second substitution reaction, which isperformed with reagent R¹—X in the presence of the substituted polymer(4) to provide the desired polymer of formula (I). For reagent R¹—X, Xis any useful leaving group (e.g., halo, hydroxyl, or sulfonate, such asmesylate, tosylate, or triflate), and R¹ is any described herein.

Finally, the fourth step includes a third substitution reaction, whichis performed with reagent R^(H)—X in the presence of the DAPP product(3) to provide a substituted polymer (II). For reagent R^(H)—X, X is anyuseful leaving group (e.g., halo, hydroxyl, or sulfonate, such asmesylate, tosylate, or triflate), and R^(H) is any described herein(e.g., R^(H) can be -L^(H)-Ar^(H) or -L^(H)-Ak^(H)).

The three substitution steps (i.e., the second, third, and fourth steps)can be performed in any order to obtain the desired substitutionpattern. Of course, if R³ and R¹ are the same substituents, then onlyone of the substitution reaction steps can be conducted. Alternatively,one or more steps may be required to install R¹ or R³ on the parentmolecule. For instance, when R¹ or R³ is —SO₂—NR^(N1)—R^(S2), multiplesteps may be required to first install the —SO₂— functional group on theparent molecule. Then, this functional group may be activated (e.g., byforming a sulfonyl halide, such as sulfonyl chloride) and reacted withan amine (e.g., NHR^(N1)—R^(S2)).

In another instance, an additional step may be required to install thefunctional group. For example, when R¹ or R³ includes two sulfonylgroups, such as in —SO₂—NR^(N1)—SO₂—R^(S2′), then then sulfonyl groupscan be attached sequentially. In one example, the method includesinstalling the first —SO₂— functional group on the parent molecule andthen reacted with a primary amine, such as NH₂R^(N1), thereby providinga parent molecule having a —SO₂—NHR^(N1) sulfonamide group. Thissulfonamide can then be reacted with an activated sulfonyl agent, e.g.,a Cl—SO₂—R^(S2′) agent, where R^(S2′) is an optionally substituted C₁₋₁₂alkyl, thereby providing an R^(S) moiety of —SO₂—NR^(N1)—SO₂—R^(S2′) onthe polymer.

In yet another instance, when R¹ or R³ is —R^(PA)—P(O)<(R^(P1)R^(P2),multiple steps may be required to first install the R^(PA) alkylene orheteroalkylene on the parent molecule, and then to later install the—P(O)<R^(P1)R^(P2) group on the alkylene or heteroalkylene molecule.Furthermore, if R^(P1) or R^(P2) is an alkoxy or aryloxy group, thenadditional step may be required to modify a hydroxyl group attached tothe phosphorous atom with an alkoxy or aryloxy group. A skilled artisanwould understand that additional modifications or step can be employedto arrive at the desired structure.

Exemplary R¹—X and R³—X reagents include HSO₃Cl, H₂SO₄, PCl₃, POCl₃,H₃PO₄, SO₃, fuming sulfuric acid, thionyl chloride, trimethylsilylchlorosulfonate, dialkyl phosphites (e.g., diethyl phosphate with anoptional catalyst, such as a Pd(0) catalyst), phosphines (e.g., tertiaryphosphines), phosphoric acids (e.g., hypophosphorous acids, phosphonicacids, phosphinic acids, etc.), aryl halide (e.g., RX, where R is anoptionally substituted aryl group, as defined herein, and X is halo),aryl halide (e.g., RX, where R is an optionally substituted aryloylgroup, as defined herein, and X is halo, such as trifluorobenzoylchloride), protein kinase (e.g., to install a phosphoryl group),phosphonoxyphenols, as well as mixtures thereof.

As discussed herein, the substitution steps can be performed in anyuseful order. In one non-limiting instance, the reaction scheme includesintroducing one or more reactive handles R^(H), and then introducingother substitution groups (e.g., R¹ and/or R³). As shown in Scheme III,the polymer of formula (II) can be formed by performing a Diels-Alderreaction to form the pendent and backbone aryl groups, performing afirst substitution reaction to introduce R^(H), performing a secondsubstitution reaction to introduce R³ to the parent structure, andperforming a final substitution reaction to introduce R¹. In oneinstance, the substitution steps including R³ and R¹ can be conducted inthe opposite order. These four steps are described in more detail below.

Similar to Schemes I and II, the first step in Scheme III includes aDiels-Alder reaction that is performed with an optionally substituteddiene, such as a 1,4-bis-(2,4,5-triphenyl cyclopentadienone)arylenereagent (1), in the presence of an optionally substituted dienophile,such as a diethynylarylene reagent (2). This reaction provides aDiels-Alder poly(phenylene) polymer (DAPP) (3).

The second step includes a first substitution reaction, which isperformed with reagent R^(H)—X in the presence of the DAPP product (3)to provide a R^(H)-substituted polymer (5). For reagent R^(H)—X, X isany useful leaving group (e.g., halo, hydroxyl, or sulfonate, such asmesylate, tosylate, or triflate), and R^(H) is any described herein(e.g., R^(H) can be -L^(H)-Ar^(H) or -L^(H)-Ak^(H)).

The third step includes a second substitution reaction, which isperformed with reagent R³—X in the presence of the R^(H)-substitutedpolymer (5), thereby providing a R^(H)-, R³-substituted polymer (6). Forreagent R³—X, X is any useful leaving group (e.g., halo, hydroxyl, orsulfonate, such as mesylate, tosylate, or triflate) and R³ is anydescribed herein.

Finally, the fourth step includes a third substitution reaction, whichis performed with reagent R¹—X in the presence of the R^(H)-,R³-substituted polymer (6) to provide the desired polymer of formula(II). For reagent R¹—X, X is any useful leaving group (e.g., halo,hydroxyl, or sulfonate, such as mesylate, tosylate, or triflate), and R¹is any described herein.

As shown in Scheme IV, the polymer reagent of formula (12) can be formedby performing a Diels-Alder reaction to form the pendent and backbonearyl groups and to install reactive end groups R^(L). Then, substitutionreactions can be performed in order to introduce R³, R¹, and/or R^(H).These three steps are described in more detail below.

Similar to that of Scheme I, the first segment is formed by performing aDiels-Alder reaction with a1,4-bis-(2,4,5-triphenylcyclopentadienone)arylene reagent (1) and adiethynylarylene reagent (2).

To further install reactive end groups, the Diels-Alder reaction is alsoperformed in the presence of a monoethynylarylene reagent (7). As can beseen, because reagent (2) includes two dienophile groups (i.e., twoethynyl groups), this reagent can react with two diene molecules (1),where the product of this reaction can further propagate thepolymerization reaction. In contrast, reagent (7) includes only onedienophile group, and therefore terminates the polymerization reactionand provides a polymer reagent (8) having a terminal reactive end groupR^(L). Additional methods for installing reactive end groups aredescribed in U.S. Pat. No. 8,110,636, which is incorporated herein byreference in its entirety.

Then, substitution reaction(s) can be performed. In Scheme IV, thesubstitution reactions are provided as three steps performed first withreagent R³—X (e.g., as described herein) in the presence of anunsubstituted polymer (8) to form a further polymer (9), then withreagent R¹—X (e.g., as described herein) to form a further polymer (10),and finally with reagent R^(H)—X (e.g., as described herein) to formpolymer reagent (12). If R³ and R¹ are the same substituents, then asingle substitution reaction step can be conducted. If R³ and R¹ aredifferent, then these substituents can be added in any desired order. Askilled artisan would understand that other modifications could be madeto form the desired polymer reagent (12). In exemplary Scheme IV, Ar^(L)in formula (12) is Ar^(L′)—(R₁)_(q), which is a non-limiting embodiment.

Methods of making the polymer also include preparing an initial polymerhaving one or more R¹ and/or R³ substituents, and then installing one ormore R^(H) on one or more pendent and/or backbone aryl groups. As seenin FIG. 23A, in one instance, the initial polymer is a sulfonated DAPPpolymer (SDAPP) having one or more sulfo groups (e.g., on one or morependent aryl groups), which can then be reacted with reagent R^(H)—X toinstall one or more R^(H) substituents on that SDAPP polymer. As alsoseen in FIG. 23A, in another instance, the initial polymer is a fullysulfonated DAPP polymer (FS-DAPP) having one or more sulfo groups (e.g.,on one or more pendent aryl groups and on one or more backbone arylgroups), which can then be reacted with reagent R^(H)—X to install oneor more R^(H) substituents on that FS-DAPP polymer.

In another instance, a precursor of the polymer herein (e.g., a polymerhaving a structure of formula (I)) is prepared as a membrane, andfurther functionalization is conducted to include one or more R^(H), R¹,and/or R³ substituents by reacting the membrane with one or morereagents to install such substituents.

Any reactions herein can be conducted with any useful reagent, solvent,or conditions. An example of reagent (1) includes1,4-bis-(2,4,5-triphenylcyclopentadienone)benzene, and an example ofreagent (2) includes diethynylbenzene reagent. Exemplary solvents usefulfor Diels-Alder and substitution reactions include an ether (e.g.,diphenyl ether), methylene chloride, dichloroethane, etc. Salts of anypolymers can be obtained by reacting any product with a suitable acid orbase to obtain the desired acid or base addition salt. Furthermore,additional reaction steps can be conducted to further purify, test, oruse any polymer herein.

Additional details on synthesis are described in Fujimoto C H et at,“Ionomeric poly(phenylene) prepared by Diels-Alder polymerization:Synthesis and physical properties of a novel polyelectrolyte,”Macromolecules 2005; 38:5010-6, Lim Y et al., “Synthesis and propertiesof sulfonated poly(phenylene sulfone)s without ether linkage byDiels-Alder reaction for PEMFC application,” Electrochim. Acta 2014;119:16-23, Hibbs M R et al., “Synthesis and characterization ofpoly(phenylene)-based anion exchange membranes for alkaline fuel cells,”Macromolecules 2009; 42:8316-21, Jakoby K et al., “Palladium-catalyzedphosphonation of polyphenylsulfone,”Macromol. Chem. Phys. 2003;204:61-7, Parcero E et al., “Phosphonated and sulfonatedpolyphenylsulfone membranes for fuel cell application,” J Membr. Sci.2006; 285:206-13, Poppe D et al., “Carboxylated and sulfonatedpoly(arylene-co-arylene sulfone)s: thermostable polyelectrolytes forfuel cell applications,” Macromolecules 2002; 35:7936-41, Akiko O etal., “Electrophilic aromatic aroylation with CF₃-bearing arenecarboxylicacid derivatives: Reaction behavior and acidic mediator dependence,”Synth. Commun. 2007; 37:2701-15, Jang D O et al., “Highly selectivecatalytic Friedel-Crafts acylation and sulfonylation of activatedaromatic compounds using indium metal,” Tetrahedron Lett. 2006;47:6063-6, Skalski T J G et al., “Structurally-defined,sulfo-phenylated, oligophenylenes and polyphenylenes,” J Am. Chem. Soc.2015; 137(38):12223-6, Kobayashi S et al., “Catalytic Friedel-Craftsacylation of benzene, chlorobenzene, and fluorobenzene using a novelcatalyst system, hafnium triflate and trifluoromethanesulfonic acid,”Tetrahedron Lett. 1998; 39:4697-700, Noji M et al., “Secondarybenzylation using benzyl alcohols catalyzed by lanthanoid, scandium, andhafnium triflate,” J. Org. Chem. 2003; 68:9340-7, Singh R P et al., “Anefficient method for aromatic Friedel-Crafts alkylation, acylation,benzoylation, and sulfonylation reactions,” Tetrahedron 2001; 57:241-7,Ellenberger F et al., “Trifluoromethanesulfonic-carboxylic anhydrides,highly active acylation agents,” Angew. Chem. Int'l Ed 1972;11(4):299-300, Effenberger F et al., “Catalytic Friedel-Crafts acylationof aromatic compounds,” Angew. Chem. Int'l Ed, 1972; 11(4):300-1, andRakira P E, “Triflic acid and its derivatives: a family of usefulreagents for synthesis,” Chem. Today 2004 May/April:48-50, as well asU.S. Pat. Nos. 8,809,483, 8,110,636 and 7,301,002, each of which isincorporated herein by reference in its entirety.

Uses

The polymers of the invention can be used in a variety ofelectrochemical applications. For instance, any polymer herein can beprepared as a membrane (e.g., by casting), and the membrane (e.g., aproton exchange membrane) can be incorporated into any device. Inanother instance, a precursor of the polymer herein (e.g., a polymerhaving a structure of formula (I)) is prepared as a membrane (e.g., ananion exchange membrane), and further functionalization is conducted toinclude one or more R^(AF) (e.g., R^(A) and/or R^(F)), R^(H), R¹, and/orR³ substituents by reacting the membrane with one or more reagents toinstall such substituents.

Exemplary devices include fuel cells (e.g., automotive fuel cells,hydrogen fuel cells, or direct methanol fuel cells), flow batteries(e.g., redox flow batteries, such as vanadium redox flow batteries),electrolyzers, electrochemical hydrogen production devices, etc. Themembranes can be used for any use, such as a proton exchange membrane,an anion exchange membrane, an ion exchange resin, a polymer separator,etc. In addition, the membranes can be in any useful form, such as ahydrogel. Membranes formed from the polymers herein can, in someinstances, display enhanced properties, such as enhanced ion exchangecapacity, decreased water uptake, and/or enhanced durability (e.g., asdetermined by stress-strain measurements). Methods of forming andtesting membranes are described in Fujimoto C H et al., Macromolecules2005; 38:5010-6, Lim Y et al., Electrochim. Acta 2014; 119:16-23, SunC-N et al., “Evaluation of Diels-Alder poly(phenylene) anion exchangemembranes in all-vanadium redox flow batteries,” Electrochem. Commun.2014; 43:63-6, Merle G et al., “Anion exchange membranes for alkalinefuel cells: A review,” J. Membrane Sci. 2011; 377:1-35, Stanis R J etal., “Evaluation of hydrogen and methanol fuel cell performance ofsulfonated Diels Alder poly(phenylene) membranes,” J. Power Sci. 2010;195:104-10, and Fujimoto C et al., “Vanadium redox flow batteryefficiency and durability studies of sulfonated Diels Alderpoly(phenylene)s,” Electrochem. Commun. 2012; 20:48-51, as well as U.S.Pat. Nos. 8,809,483, 8,110,636, and 7,888,397, each of which isincorporated herein by reference in its entirety.

EXAMPLES Example 1 Fluorine-Containing Anion Exchange Membranes

Anionic exchange membranes generally employ materials having a cationiccharge in order to bind to anions, However, one recent hurdle in use ofsuch anion exchange membranes in fuel cells has been the high wateraffinity of these materials due to the cationic charge. High wateraffinity results in poor fuel cell performance at high current densitysince the water created in the fuel cell is not rejected, and thenblocks incoming hydrogen and air from reaching the catalytic sites. Thisresults in flooding. We proposed using halo groups (e.g., fluoro) withinthe anion exchange polymer structure, which should improve thehydrophobic properties and resist flooding problems. One synthesis issueis that fluorine incorporation is typically difficult and requiremulti-step reactions.

Provided herein are compositions and methods including suchhalo-containing polymers that also include a cationic moiety, therebyenabling its use as an anion exchange membrane. We discuss methods toattach both fluorine and benzyl halide groups onto the Diels-Alderbackbone. In FIG. 11, the first step is to attach the trifluorobenzoylgroups onto the poly(phenylene) backbone (e.g., catalyzed by triflicacid). The resultant polymer (IV-6) can be isolated and dried before thenext step, but these reactions can be combined to a one pot (one step)process in which both acid chlorides are added at the same time. Thesynthesized polymer (IV-7) can include both the fluoro-containingfunctional groups and the chloro-containing functional groups. In FIG.11, the fluorine in the poly(phenylene) backbone is not required butused herein as a reference for NMR characterization.

As seen in FIG. 12, the resultant polymer (IV-7) can be cast as a filmand then soaked in aqueous trimethyl amine to provide a cationic polymer(IV-8). Alternatively, as seen in FIG. 13, the polymer (IV-7) can bedissolved in a solvent (e.g., tetrahydrofuran, THF), reacted with atrimethyl amine to provide the cationic polymer (IV-8), and then castgenerate the trimethyl benzyl ammonium group.

Furthermore, any other useful synthetic steps can be employed to modifyany portion of the polymer. In one non-limiting instance, a ketonefunctional group can be sensitive to attach by a nucleophile (e.g., ahydroxide anion), and such a ketone group can be removed from the linkerin any useful manner. In one instance, the ketone functional group isreduced prior to attaching the ammonium cation (FIG. 14), therebyproviding interim polymer (IV-9) including chloro- and fluoro-groupsthat can be further reacted to provide a cationic polymer (IV-10).

Any useful reagents can be employed. For instance, for the reduction ofketone groups, refluxing in 1,2 dichloroethane (DCE) with triethylsilane and trifluoroacetic acid is sufficiently gentle enough tominimize side reactions with the benzyl chloride groups. After reductionof the ketone, the resultant polymer can either be cast as a film ordissolved in a solvent (e.g., THF) to react with an amine (e.g., atrialkyl amine, such as NMe₃) to form the ammonium cation.

A lengthy linker between the pendent aryl group and the cationic moietycan also be incorporated by first attaching an alkyl chloride group inthe optional presence of a Lewis acid catalyst (e.g., a 6-bromohexanoylchloride in the presence of aluminum trichloride), then attachment of ahalo-containing aryl group in the presence of an acid catalyst (e.g., atrifluorobenzoyl chloride with triflic acid), followed by ketonereduction, and then reaction with an amine to provide a cationic moiety(e.g., reaction with a trialkyl amine, such as NMe₃). An exemplarypolymer (IV-11) provided by such a synthetic scheme is provided in FIG.15.

Example 2 Testing of Anion Exchange Membranes

Anion exchange membranes have been developed using poly(phenylene)polymers formed by a Diels-Alder reaction (Diels-Alder polyphenylenepolymers, DAPPs). In particular, such a synthesis allows for use ofpoly(phenylene) polymers as the backbone scaffold. FIG. 6A shows anexemplary poly(phenylene)-based polymer, which displays high backbonestability under alkaline conditions (FIG. 7A). Without wishing to belimited by mechanism, the presence of aryl-aryl bonds provide such astability as these bonds are less likely to be cleaved, as compared tobonds within heteroatom-containing polymers, such as poly(aryleneether)s (FIG. 6B). As can be seen, stress strain curves are provided fora DAPP (FIG. 7A) and a poly(arylene ether) (FIG. 7B) under varyingalkaline conditions. The DAPP-based anion exchange polymer displayedenhanced mechanical stability under tested conditions, as compared tothe poly(arylene ether) polymer. Accordingly, DAPP-based polymersdisplay particular mechanical characteristics imparted by the backbone.It is believed that a DAPP-based polymer can be further modified toprovide other chemical characteristics, such as by installing a cationicmoiety to impart binding to anions or by installing a hydrophobic moiety(e.g., a halo) to provide a membrane with lower water affinity. Suchpolymer can, for instance, have a structure of formula (I).

Example 3 Functionalization of Diels-Alder Polyphenylene Polymers

Friedel-Crafts acylation reactions can be employed to functionalizeDiels-Alder polyphenylene polymers (see, e.g., U.S. Pat. No. 8,809,483).Such functionalized polymers can be further reacted to provide anyuseful polymer (e.g., a polymer having formula (I)). As seen in FIG.25A, a Diels-Alder poly(phenylene) polymer (DAPP) is functionalized byway of a Friedel-Crafts acylation reaction with an alkyl acyl chloride(e.g., 6-bromohexanoyl chloride) in the presence of aluminum trichlorideas a catalyst, thereby providing an alkyl acylated DAPP.

When this Friedel-Crafts acylation approach was used to attach aryl acylchlorides (e.g., benzoyl chloride), an insoluble product was obtained,which could not be processed further (FIG. 25B, top reaction pathway).Without wishing to be limited by mechanism, Lewis acids, such as FeCl₃and AlCl₃, are known to catalyze oxidative carbon-carbon (C—C) coupling,including intramolecular and intermolecular C—C coupling, as well asaryl-aryl coupling, such as in a Scholl reaction. Such couplingreactions are not desired and may lead to insoluble polymeric products.Due to the insolubility of the product provide by the reaction in FIG.25B (top reaction pathway), we believe that only a trace amount ofintramolecular or intermolecular C—C coupling of pendent aryl groups inDAPP would result in insoluble cross linking. Common trace impurities inAlCl₃, such as FeCl₃ and acidic protons, are potential catalysts forthis process.

There are numerous differences between an alkyl acylation reaction(e.g., as in FIG. 25A) and an aryl acylation reaction (e.g., as in FIG.25B). Without wishing to be limited by mechanism, the reaction pathwaydifference between alkyl and aryl acyl chlorides can be explained interms of the stability of the acylium ion intermediates. An aryl acyliumion is stabilized by resonance delocalization, which is not available inalkyl acylium. Thus, the alkyl acylium ion is readily nucleophilicallyattacked by the pendent aryl groups of DAPP, while the aryl acylium ionreacts slower with the aryl groups so that it competes with aryl-arylcoupling (see, e.g., Corriu R et at, “Mécanisme de la C acylation: étudecinétique du mécanisme de l'acétylation des composés aromatiquescatalysée par AlCl₃,” Tetrahedron 1971; 27:5819-31; and Corriu R et al.,“Mécanisme de la C acylation: étude cinétique du mécanisme de labenzoylation des composés aromatiques catalysée par AlCl₃,” Tetrahedron1971; 27:5601-18). Due to these differences in stability between thealkyl-based versus aryl-based ions, different reaction pathways anddifferent end-products can be observed.

New strategies were required to effectively attach aryl-based functionalgroups on DAPP backbone and/or pendent groups. In particular, thesedevelopments included use of a metal salt to promote aryl acylation.Effenberger published work discussing non-metal catalyzed, FriedelCrafts acylation employing silver triflate (see Effenberger F et al.,“Trifluoromethanesulfonic-carboxylic anhydrides, highly active acylationagents,” Angew. Chem. Int'l Ed. 1972; 11(4):299-300). Without wishing tobe limited by mechanism, a reaction between silver triflate and benzoylchloride generally generates a trifluoromethanesulfonic-carboxylicanhydride and silver chloride (FIG. 25C). The anhydride can then furtherreact with arenes, such as benzene or a phenyl ring to form benzophenoneat high yields (e.g., a yield of about 90% or greater). One disadvantageof utilizing silver triflate in this manner is that for every aryl acylchloride, at least one equivalent of silver triflate is required. Analternative to silver triflate, is employing triflic acid; only acatalytic amount (e.g., 1%) can be used for the Friedel Crafts acylationof aryl acyl chlorides (see, e.g., Effenberger F et al., “CatalyticFriedel-Crafts acylation of aromatic compounds,” Angew. Chem. Int'l Ed.1972; 11(4):300-1).

We have applied this chemistry onto a Diels-Alder polyphenylene (DAPP)by reacting a F-labeled DAPP with 4-fluorobenzoyl chloride in thepresence of sliver triflate (FIG. 26A), thereby producing a DAPP havingone or more reactive handles (II-13). By using 19F-NMR and a fluorine inthe polymer backbone as a reference, we can monitor the amount oftrifluoromethylbenzoyl that is attached to the backbone (see, e.g., FIG.26B). Any useful reaction conditions can be modified to increase yield.For instance, reaction temperatures can be increased (e.g., of fromabout 60° C. or greater, such as of from about 60° C. to about 140° C.);solvent or solvent mixtures can be modified (e.g., by use of no solventor by use of solvents with low donor numbers, e.g., ethers, acetone,aprotic solvents, non-polar solvents, polar aprotic solvents, etc.); andconcentration of reactants can be altered to maximize yield and/orselectivity.

The synthetic protocol is provided in FIG. 26A and was conducted asfollows. Two g of F-labeled DAPP (2.59 mmol) was dissolved in 20 mL ofmethylene chloride, and 1.63 g of 4-fluorobenzoyl chloride (10.3 mmol)was added to this yellow solution. The yellow solution was cooled in anice bath, and 2.64 g of silver triflate (10.3 mmol) was added in oneaddition to give a dark brown color. After 1 hour, the ice bath wasremoved; and the reaction was stirred overnight at room temperature.Next day, the solution was added to water and heated to boil off theorganic solvent. The remaining solid was then collected, rinsed withwater several times, and dried in a vacuum oven overnight at 60° C.

The resultant product was dissolved in D-chloroform for 19F-NMR analysisto determine fluorine quantitative incorporation (FIG. 26B). The signalat −105 ppm arose from the pendent fluorine on the carbonyl aryl group,while the peak at −115 ppm corresponded to a backbone fluorine. Usingthe peak at −115 ppm as a reference signal, we estimated that about 2.6pendent aryl fluorine groups were functionalized per repeat group.

The aryl fluorine group can serve as a reactive handle, which can befurther reacted with other functional groups. In particular, thefunctional versatility of attaching the 4-fluorobenzoyl group is thelability of aryl halides in the presence of a strong electronwithdrawing group towards nucleophilic aromatic substitution (SnAr2). Asseen in FIG. 26C, the labile aryl halide of the DAPP having a reactivehandle (II-13) can be reacted with an aryl ether to append the ether byway of an SnAr2 reaction, thereby forming the further functionalizedDAPP polymer (II-14).

Example 4 Acylation Using an Arylsulfonyl Reagent

FIG. 27 provides another exemplary reagent to provide a functionalizedDAPP polymer. As described herein, the reagent to provide the reactivehandle can have the formula R^(H)X, in which R^(H) can have the formula-L^(H)-Ar^(H) or -L^(H)-Ak^(H) (e.g., any described herein). In oneinstance, the exemplary R^(H)—X reagent is Ar^(H)-L^(H)-X, in whichL^(H) is a sulfonyl and Ar^(H) is an optionally substituted aryl. Asseen in FIG. 27, the R^(H)—X agent includes a linker L^(H) that issulfonyl (—SO₂—) and an aryl group Ar^(H) that is a fluorinated phenyl.The Ar^(H) group can serve as an Ar^(AF) group (e.g., an aryl groupincluding a cationic moiety or a halo).

The reactive handle R^(H) can be installed in any useful manner. In oneinstance, R^(H) can be reacted with the F-labeled DAPP in the presenceof a metal salt, e.g., M(OTf), a metal triflate salt. The metal triflatecan promote the Friedel Crafts aryl acylation reaction, therebyproviding an exemplary DAPP polymer (II-15) having one or more R^(H)groups appended to the pendent aryl groups and/or the backbone arylgroups of the DAPP polymer.

Example 5 Synthesis of the Fluorinated Diels-Alder Poly(phenylene)F-DAPP (3*)

FIG. 28 provides the first step for a synthetic scheme, which provides afluorinated Diels-Alder poly(phenylene) F-DAPP (3*). To 16.9 g ofbis(teracyclone) [24.5 mmol] (1*) and 3.5 g of 1,4diethyny-2-fluorobenzene [24.5 mmol] (2*) in a 500 mL three neck roundbottom flask was added 250 mL of diphenyl ether. The reaction vessel washeated to 165° C. under N₂. After 24 hours, the reaction vessel wascooled; and the orange, viscous medium was precipitated from acetone.The solid was isolated, dried, and dissolved in toluene (10 mL oftoluene per gram) and then re-precipitated from acetone. The resultantpowder was isolated and dried in a vacuum oven at 150° C. for 48 hours,thereby providing F-labeled DAPP (3*).

Example 6 Acylation of Diels-Alder Poly(phenylene) Backbone With SilverTriflate

FIG. 28 also provides the second step for a synthetic scheme, whichprovides a Diels-Alder poly(phenylene) having a reactive handle composedof a fluorinated acyl group (II-16). Under N₂, 2 g of the fluorinatedDiels-Alder poly(phenylene) (3*) [2.6 mmol] was dissolved in 150 mL of1,2-dichloroethane in a 500 mL three neck round bottom flask. At roomtemperature, 2.4 g of 4-fluorobenzoyl chloride [15.2 mmol] and 3.9 g ofAgOTf [15.2 mmol] were added to the reaction vessel. The color of thesolution changed from an initial yellow solution to a dark red solution.The reaction was heated to 50° C. for 16 hours. The resultant slurry wasfiltered by passing through a 2 μm glass fiber syringe frit to removeexcess AgOTf and AgCl. The red solution was then precipitated fromreagent ethanol and dried in a vacuum oven at 150° C. for 24 hours toprovide a fluoroacylated DAPP compound (II-16).

Other embodiments

All publications, patents, and patent applications mentioned in thisspecification are incorporated herein by reference to the same extent asif each independent publication or patent application was specificallyand individually indicated to be incorporated by reference.

While the invention has been described in connection with specificembodiments thereof, it will be understood that it is capable of furthermodifications and this application is intended to cover any variations,uses, or adaptations of the invention following, in general, theprinciples of the invention and including such departures from thepresent disclosure that come within known or customary practice withinthe art to which the invention pertains and may be applied to theessential features hereinbefore set forth, and follows in the scope ofthe claims.

Other embodiments are within the claims.

1. A composition comprising a structure having the formula (I):

or a salt thereof or a form thereof including a counter ion, wherein:each and every R^(AF) comprises a cationic moiety or a halo; each R¹ andR³ is, independently, H, halo, optionally substituted C₁₋₁₂ alkyl,optionally substituted C₁₋₁₂ haloalkyl, optionally substituted C₁₋₁₂perfluoroalkyl, optionally substituted C₁₋₁₂ heteroalkyl, R^(S), R^(P),R^(C), or R^(E), wherein R^(S) is an acidic moiety comprising a sulfonylgroup, R^(P) is an acidic moiety comprising a phosphoryl group, R^(C) isan acidic moiety comprising a carbonyl group, and R^(E) is anelectron-withdrawing moiety; each Ar^(L) is, independently, a bivalentlinker comprising optionally substituted arylene; each Ar^(M) is,independently, a bivalent linker comprising optionally substitutedarylene; each q is, independently, an integer of from 0 to 5; each a is,independently, an integer of from 0 to 5, wherein at least one a is not0; and m is an integer of from about 1 to
 1000. 2. The composition ofclaim 1, wherein at least one R^(AF) is an aryl, an alkyl, or aheteroalkyl substituted with the cationic moiety.
 3. The composition ofclaim 1, wherein the cationic moiety comprises an onium cation.
 4. Thecomposition of claim 3, wherein the onium cation comprises an ammoniumcation.
 5. The composition of claim 1, wherein at least one R^(AF) is anaryl, an alkyl, or a heteroalkyl substituted with the halo.
 6. Thecomposition of claim 1, wherein at least one R^(AF) is an optionallysubstituted C₁₋₁₂ alkyl, optionally substituted C₁₋₁₂ haloalkyl,optionally substituted C₁₋₁₂ perfluoroalkyl, optionally substitutedC₁₋₁₂ heteroalkyl, halo, optionally substituted C₄₋₁₈ aryl, optionallysubstituted C₁₋₁₂ alk-C₄₋₁₈ aryl, optionally substituted C₄₋₁₈aryl-C₁₋₁₂ alkoxy, optionally substituted C₄₋₁₈ aryloxy, optionallysubstituted C₅₋₁₉ aryloxycarbonyl, optionally substituted C₅₋₁₉ aryloyl,optionally substituted C₄₋₁₈ arylcarbonyl-C₁₋₁₂ alkyl, optionallysubstituted C₄₋₁₈ arylsulfonyl, or optionally substituted C₄₋₁₈arylsulfonyl-C₁₋₁₂ alkyl.
 7. The composition of claim 6, wherein eachand every R^(AF) comprises an optionally substituted aryl group.
 8. Thecomposition of claim 1, wherein: at least one R^(AF) is -L^(A)-Ar^(AF)and/or -L^(A)-Ak^(AF), or a salt thereof or a form thereof including acounter ion; L^(A) is a covalent bond, carbonyl, oxy, thio, azo,phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sulfonamide, imino, imine,phosphine, nitrilo, optionally substituted C₁₋₁₂ alkylene, optionallysubstituted C₁₋₁₂ alkyleneoxy, optionally substituted C₁₋₁₂heteroalkylene, optionally substituted C₁₋₁₂ heteroalkyleneoxy,optionally substituted C₄₋₁₈ arylene, or optionally substituted C₄₋₁₈aryleneoxy; Ar^(AF) is an optionally substituted aryl comprising thecationic moiety or the halo; and Ak^(AF) is an optionally substitutedalkyl comprising the cationic moiety or the halo; or an optionallysubstituted heteroalkyl comprising the cationic moiety or the halo. 9.The composition of claim 8, wherein L^(A) is a covalent bond, carbonyl,sulfonyl, —NR^(L3)—, —(CR^(L1)R^(L2))_(La)—, —C(O)NR^(L3)—,—NR^(L3)C(O)—, —SO₂—NR^(L3)—, —NR^(L3)—SO₂—,—(CR^(L1)R^(L2))_(La)—C(O)—NR^(L3)—,—(CR^(L1)R^(L2))_(La)—NR^(L3)—C(O)—, —(CR^(L1)R^(L2))_(La)—SO₂—NR^(L3)—,or —SO₂—NR^(L3)—(CR^(L1)R^(L2))_(La)—; wherein each of R^(L1), R^(L2),and R^(L3) is, independently, H, optionally substituted alkyl,optionally substituted haloalkyl, optionally substituted alkoxy,optionally substituted alkaryl, optionally substituted aryl, or halo;and wherein Ar^(AF) or Ak^(AF) is optionally substituted with one ormore substituents selected from the group consisting of halo, cyano,optionally substituted haloalkyl, optionally substituted perfluoroalkyl,optionally substituted nitroalkyl, and optionally substituted alkyl. 10.The composition of claim 8, wherein the composition comprises astructure having any one of formulas (Ia) to (Ij), or a salt thereof ora form thereof including a counter ion; and wherein R^(AF) is R^(A)comprising the cationic moiety or R^(F) comprising the halo.
 11. Thecomposition of claim 1, wherein: R^(S) is —SO₂—R^(S1) or—SO₂—NR^(N1)—R^(S2) or —SO₂—NR^(N1)—SO₂—R^(S3), wherein each R^(S1) is,independently, H, optionally substituted alkyl, optionally substitutedhaloalkyl, optionally substituted perfluoroalkyl, optionally substitutedaryl, optionally substituted alkaryl, or hydroxyl; each R^(N1) is,independently, H or optionally substituted C₁₋₁₂ alkyl, optionallysubstituted aryl, or optionally substituted alkaryl; each R^(S2) is,independently, H, hydroxyl, optionally substituted alkyl, optionallysubstituted alkylsulfonyl, optionally substituted aryl, or optionallysubstituted alkaryl; and each R^(S3) is, independently, H, hydroxyl,optionally substituted alkyl, optionally substituted C₁₋₁₂ haloalkyl,optionally substituted perfluoroalkyl, optionally substituted aryl, oroptionally substituted alkaryl; R^(P) is —P(O)(OH)₂ or —O—PO(OH)₂ or—P(O)<R^(P1)R^(P2) or —P(O)<R^(Ar)R^(P2) or —P(O)<R^(Ar)R^(Ar), andwherein each of R^(P1) and R^(P2) is, independently, optionallysubstituted alkyl, optionally substituted alkoxy, optionally substitutedaryl, optionally substituted alkaryl, optionally substituted aryloxy,hydroxyl, or H; and each of R^(Ar) is, independently, optionallysubstituted aryl, optionally substituted alkaryl, or optionallysubstituted aryloxy; R^(C) is —CO₂H, —C(O)—R^(C1), or—R^(CA)—C(O)—R^(C1), and wherein each R^(C1) is, independently,optionally substituted alkyl, optionally substituted alkoxy, optionallysubstituted aryl, optionally substituted alkaryl, optionally substitutedaryloxy, hydroxyl, or H; and each R^(CA) is, independently, oxy,optionally substituted alkylene, or optionally substitutedheteroalkylene; and R^(E) is optionally substituted aryloyl,carboxyaldehyde, optionally substituted alkanoyl, or optionallysubstituted alkyl.
 12. The composition of claim 1, wherein Ar^(L) and/orAr^(M) is optionally substituted phenylene, optionally substitutednaphthylene, or optionally substituted phenanthrylene.
 13. Thecomposition of claim 12, wherein the optional substitution for Ar^(L) isR^(AF), R^(H), R^(S), R^(P), R^(C), or R^(E); and wherein the optionalsubstitution for Ar^(M) is R^(AF), R^(H), R^(S), R^(P), R^(C), R^(E), ora label.
 14. The composition of claim 1, wherein the compositioncomprises a structure having any one of formulas (I-1) to (I-8), (IV-3),(IV-5), (IV-8), (IV-10), or (IV-11), or a salt thereof or a form thereofincluding a counter ion; wherein each and every R^(AF1), if present,comprises the cationic moiety or the halo; wherein each and everyR^(A1), if present, comprises the cationic moiety; wherein each andevery R^(F1), if present, comprises the halo; wherein L^(A) is acovalent bond, carbonyl, oxy, thio, azo, phosphonoyl, phosphoryl,sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, nitrilo,optionally substituted C₁₋₁₂ alkylene, optionally substituted C₁₋₁₂alkyleneoxy, optionally substituted C₁₋₁₂ heteroalkylene, optionallysubstituted C₁₋₁₂ heteroalkyleneoxy, optionally substituted C₄₋₁₈arylene, or optionally substituted C₄₋₁₈ aryleneoxy; and wherein m is aninteger of from about 1 to
 500. 15. The composition of claim 14,wherein: R^(F1) is the halo, an optionally substituted aryl having thehalo, an optionally substituted alkyl having the halo, or an optionallysubstituted heteroalkyl having the halo; and/or R^(A1) is the cationicmoiety, an optionally substituted aryl having the cationic moiety, anoptionally substituted alkyl having the cationic moiety, or anoptionally substituted heteroalkyl having with the cationic moiety. 16.A composition comprising a structure having the formula (VI) or (VII):

or a salt thereof or a form thereof including a counter ion, wherein:each and every R^(AF) comprises a cationic moiety or a halo; each R¹ andR³ is, independently, H, halo, optionally substituted C₁₋₁₂ alkyl,optionally substituted C₁₋₁₂ haloalkyl, optionally substituted C₁₋₁₂heteroalkyl, optionally substituted C₁₋₁₂ perfluoroalkyl, R^(S), R^(P),R^(C), or R^(E), wherein R^(S) is an acidic moiety comprising a sulfonylgroup, R^(P) is an acidic moiety comprising a phosphoryl group, R^(C) isan acidic moiety comprising a carbonyl group, and R^(E) is anelectron-withdrawing moiety; each Ar^(L) is, independently, a bivalentlinker comprising optionally substituted arylene; each Ar^(M) is,independently, a bivalent linker comprising optionally substitutedarylene; each q is, independently, an integer of from 0 to 5; each a is,independently, an integer of from 0 to 5, wherein at least one h is not0; each of m and n is, independently, an integer of from about 1 to1000; L′ is a sublink; Ar* is a hydrophobic segment; and each R^(L) is,independently, a reactive end group.
 17. The composition of claim 16,wherein L′ comprises a covalent bond, optionally substituted C₁₋₁₂alkylene, optionally substituted C₁₋₁₂ alkyleneoxy, optionallysubstituted C₁₋₁₂ heteroalkylene, optionally substituted C₁₋₁₂heteroalkyleneoxy, optionally substituted C₄₋₁₈ arylene, optionallysubstituted C₄₋₁₈ aryleneoxy, optionally substituted polyphenylene, or astructure of formula (II).
 18. The composition of claim 16, whereinR^(L) is optionally substituted C₇₋₁₁ aryloyl or optionally substitutedC₆₋₁₈ aryl.
 19. The composition of claim 16, wherein the compositioncomprises a structure having the formula (VIa) to (VId), or a saltthereof or a form thereof including a counter ion; or the formula (VIII)or (VIIIa), or a salt thereof or a form thereof including a counter ion.20. An anion exchange membrane comprising the composition of claim 1.